Metal complexes bearing triazenide ligands and their use for depositing metals from the gas phase - Patents.com

Abstract

To provide a method and a compound useful for depositing a metal and a metal-containing layer in a gas phase.SOLUTION: The invention relates to the use of a metal complex, which has at least one ligand of the formula R1-N3-R2, wherein R1 and R2 are hydrocarbon moieties, for depositing the metal or a compound of the metal from the gas phase. The invention further relates to methods for depositing metals from the metal complexes, and to metal complexes, substituted triazene compounds and methods for the production thereof.SELECTED DRAWING: Figure 14

Description

[Technical Field]

[0001] The present invention relates to a compound of formula R for depositing a metal or another compound of a metal from the gas phase. 1 -N3-R 2 [In the formula, R 1 and R 2 is a hydrocarbon group, especially an alkyl group. The present invention further relates to a method for depositing metals from metal complexes, as well as to metal complexes, substituted triazenide compounds, and methods for their preparation. [Background technology]

[0002] Conventional technology Metalorganic vapor phase deposition, and in particular metalorganic vapor phase epitaxy, is an important method for producing thin layers of metals or metal compounds on a substrate. These methods are particularly used in the semiconductor industry. In this process, an organometallic compound, optionally in combination with additional reactive compounds, is introduced into a processing chamber, and a reaction occurs on the surface of a heated substrate under reduced or normal pressure, resulting in the deposition of a layer. In such methods, multiple metal-containing layers, such as semiconductor crystals, amorphous layers, metal compound or metal layers, may be deposited on a substrate. A review can be found, for example, in "Handbook of Thin Film Deposition - Processes and Technologies," 2nd Edition 2001, editor: Krishna Sesha, Chapter 4, pp. 151-203.

[0003] For many applications, particularly in the semiconductor industry, it is essential that such metal-containing layers be produced with high purity, as even small trace impurities can impair their intended use.

[0004] However, only very few organometallic precursor compounds are suitable for producing high-purity metal-containing layers. This is often due to the fact that suitable organometallic precursor compounds must be capable of being transferred to the gas phase at high temperatures. However, many organometallic compounds are thermally unstable. They cannot be converted to the gas phase by heating or other methods because they decompose (decompose) at higher temperatures. In this regard, a problem is that organometallic compounds are often solids with relatively high evaporation temperatures at which decomposition processes occur, especially due to reactive organic ligands.

[0005] If the organometallic compound can be vaporized, the temperature of the gas phase above the substrate, i.e., the deposition target, is usually further increased until decomposition occurs. However, even organometallic compounds that can be converted to the gas phase are often not suitable for metal deposition. This is because the deposition of metals onto the substrate surface must be carried out in a manner that does not produce impurities, even trace amounts, due to components of the complexing ligands, such as carbon, nitrogen, or oxygen. This requirement is also often not met, because the required high decomposition temperatures often result in the formation of a mixture of highly reactive intermediates, ionic radicals, and free radicals, which often cause undesirable side reactions on the substrate surface.

[0006] Metal alkyl compounds are often used as precursor compounds for depositing metal-containing layers in the gas phase. A summary of suitable compounds is contained in the above-mentioned publication by J. Zilko. However, many metal alkyl compounds often have properties that make them unsuitable for deposition reactions in the gas phase. On the other hand, many pure metal alkyl compounds of transition metals are disadvantageous in that they are unstable, easily decayed, and cannot be stored. On the other hand, they tend to undesirably introduce anionic carbon, which is bound to the transition metal, into the layer. They also often have relatively high evaporation temperatures, which are disadvantageous for use in vapor deposition.

[0007] Thus, there is a continuing need for improved methods and materials for depositing metal and metal-containing layers by metalorganic vapor deposition.

[0008] Metal-organic complexes containing N-aryl and N,N'-diaryl-triazenide ligands are known in the prior art. However, the use of such complexes for depositing metals from the gas phase has not been disclosed in the prior art. This is not surprising, since metal complexes containing these ligands do not have sufficient volatility and decomposition properties, which are essential for use in depositing metals from the gas phase. Therefore, such reactions can result in non-volatile carbon impurities.

[0009] Metal-organic complexes containing aromatically substituted triazenide ligands have been described in various publications, however, virtually all of these publications relate only to the synthesis and structure of such complexes, and practical applications of the compounds are described only in exceptional cases.

[0010] Methods for providing differently substituted precursor compounds of triazenide anions are known. In 1981, Brand and Roberts described the electronic configuration of the 1,3-dialkyltriazenyl group and stated in a footnote that starting from tert-butyl azide and tert-butyl lithium, this could represent di-tert-butyltriazine. Neither experimental nor spectroscopic data were published. [1] Ethyl and methyl substituted triazenes were also described by Smith and Michejda in 1983, with synthesis carried out with either methyllithium or the Grignard reagent ethylmagnesium bromide. [2] Furthermore, the synthesis of different alkyl- and aryl-substituted triazenes and studies on tautomeric equilibria have been discussed in various publications. [3,4]

[0011] Alkaline earth and alkali metal compounds of triazenes are known only from aryl-substituted systems. All crystallographically characterized compounds in publications are solvates and / or compounds in which the corresponding metal is stabilized by TMEDA or

[15] -Crown-5. [6~10]

[0012] Triazenide compounds with group III main group elements have been known from the literature for several decades.

[0013] U.S. Patent No. 3,386,985 describes various organometallic compounds having various triazenide ligands, particularly 1,3-dimethyltriazine. The compounds are proposed for use as chain transfer agents or inhibitors in polymerization processes. No metal deposition methods are described.

[0014] Brinckman et al.

[11] describe organometallic complexes having 1,3-dimethyltriazenide as a ligand, and the results are largely consistent with those contained in U.S. Pat. No. 3,386,985. No further explanation is given regarding the practical use of the complexes. The production process still requires improvement, as the yield is less than 76%.

[0015] In addition, a variety of complexes bearing one and / or two aryl-triazenide ligands, both homoleptic and heteroleptic, have been described in the literature. [12~16]

[0016] In the transition metal area, several triazenide compounds with aromatically substituted ligands are known and have been investigated with early transition metals such as titanium and zirconium, as well as late transition metals such as silver and copper as central atoms. [6,17~23] Both homoleptic and heteroleptic molecular or cationic cobalt complexes with aromatically substituted triazenide ligands have been described in conjunction with ESR measurements. Ruthenium compounds have also been reported in conjunction with theoretical calculations. [24~30]

[0017] Soussi et al. [5] described the preparation of organometallic iron complexes with alkyl triazenides as ligands and TMEDA (tetramethylethylenediamine) ligands for stabilization. The complexes are prepared via a relatively complex ligand exchange route, starting from Fe[N(SiMe3)2]2. The metal complexes are used to produce intermetallic nanoparticles. The evaporation and decomposition behavior of the iron complexes as the temperature increases is investigated by thermogravimetric analysis. It was found that four metal complexes could not be vaporized due to their low thermal stability. When the temperature was increased above 200 °C, solid residues remained, accounting for approximately 20–40 wt% of the sample weight. In addition, when the temperature was increased up to 200 °C, the weight curves showed an irregular course, typical of chemical decomposition reactions. Therefore, the metal complexes are not suitable as precursor compounds for the production of metal-containing vapor-phase coatings.

[0018] Various rare earth metal complexes are known from the literature, but only with sterically very demanding aryl-triazenide ligands. [31~33] [Prior art documents] [Patent documents]

[0019] [Patent Document 1] U.S. Patent No. 3,386,985 [Patent Document 2] U.S. Patent No. 3,386,985 [Non-patent literature]

[0020] [Non-Patent Document 1] Handbook of Thin Film Deposition-Processes and Technologies” 2nd Edition 2001, editor:Krishna Sesha,Chapter4,pp.151-203 Summary of the Invention [Problem to be solved by the invention]

[0021] There is a continuing need in the art for methods and compounds useful for depositing metal and metal-containing layers in the vapor phase that overcome the above-mentioned drawbacks.

[0022] Object of the invention The present invention is based on the object of providing methods and compounds which overcome the above-mentioned drawbacks. In particular, the present invention is based on the object of providing new and improved compounds for depositing metal and metal-containing layers from the gas phase.

[0023] The compound must have a relatively high stability. The compound must have a high vapor pressure and at the same time a low decomposition point. The compound must be convertible to the gas phase without substantial decomposition. After conversion to the gas phase, i.e., at a temperature above the sublimation or evaporation temperature, the compound must be decomposed. Decomposition preferably occurs at a temperature slightly above the sublimation or evaporation temperature.

[0024] The compounds generally must have high stability and volatility at temperatures at which deposition methods from the vapor phase are usually carried out, particularly at temperatures between 100° C. and 300° C. In particular, the compounds must be sublimable.

[0025] The present invention is based in particular on the object of providing compounds that can be stably converted into the gas phase at temperatures up to 100°C and can be decomposed at higher temperatures, for example in the range of 100°C to 400°C.

[0026] The compounds are intended to allow deposition of a variety of metals and metal-containing compounds from the vapor phase. The coatings must be highly purified. In particular, the coatings must be free of undesirable carbon, oxygen, or nitrogen contamination that occurs with conventional deposition methods.

[0027] The present invention is further based on the objective of providing a method for producing such compounds that is as simple and efficient as possible. The reagents used should be as readily available and safe to handle as possible. It should be possible to carry out the method with high yields. The method should lead to the desired product in as few steps as possible and should be able to be carried out under as mild reaction conditions as possible. It is also intended to provide compounds from which volatile precursor compounds can be prepared in the simplest possible way. [Means for solving the problem]

[0028] Disclosure of the Invention Surprisingly, the object on which the present invention is based is solved by the applications, methods, metal complexes and further compounds according to the present claims. DETAILED DESCRIPTION OF THE INVENTION

[0029] The object of the present invention is to provide a compound of formula R 1 -N3-R 2 [In the formula, R 1 and R 2 is a hydrocarbon group] for depositing a metal or metal compound from the gas phase. In this case, the N3 subunit has a negative charge, so the ligand L is formally an anionic ligand.

[0030] In this case, a solid layer consisting of or containing a metal is deposited on a substrate from the gas phase. The metal complex is used as an organometallic precursor compound (precursor). The metal from the metal complex is deposited in a targeted manner in the form of an element or a compound of the metal. Thus, for example, nitrogen from a ligand or from a suitable reactant partner can be incorporated into the layer, resulting in the formation of a nitride of the deposited metal. Preferably, the metal complex is first converted into the gas phase, or at least a volatile intermediate product containing the metal is converted into the gas phase. In the gas phase, the temperature is usually further increased under reduced pressure, resulting in (further) decomposition of the metal complex. The decay can also be stimulated or assisted in different ways, for example, by radiation. The crucial decomposition of the metal complex only needs to occur after conversion into the gas phase. This ensures that the metal complex is present as quantitatively as possible in the gas phase and can be used to deposit the metal or metal compound. Furthermore, if controlled decomposition occurs only in the gas phase, the number of undesired side reactions can be regularly reduced.

[0031] In a preferred embodiment, the metal complex has the formula R 1 -N3-R 2 The compound has at least one ligand L and at least one further ligand X. The further ligand X is preferably selected from halogen, H, CO, and hydrocarbon ligands. The hydrocarbon ligand is in particular an alkyl or alkenyl having 1 to 12 carbon atoms and an aromatic hydrocarbon having 5 to 30 carbon atoms. The hydrocarbon ligand may be neutral or may carry a negative charge. The halogen may be F, Cl, Br, or I, with Cl being particularly preferred. When X=H, a hydride complex is present. This complex may have one or more ligands X, for example one, two, or three ligands X. In this case, it is preferred that exactly one or two ligands X are present. When two or more ligands X are present, the ligands X may be identical to or different from one another.

[0032] In a preferred embodiment, the metal complex has the formula R 1 -N3-R 2 [In the formula, R1 and R 2 is an alkyl group.

[0033] In a preferred embodiment, the metal complex has the formula (1): M x [(L 1 ) a (L 2 ) b (L 3 ) c X d ](1) [In the formula, L 1 , L 2 and L 3 The ligand L is of the formula R 1 -N3-R 2 (In the formula, R 1 and R 2 are independently selected from the group At least L 1 Regarding R 1 Groups and R 2 The group is an alkyl group, X is independently selected from H, halogen, CO, and hydrocarbon ligands, in particular alkyl groups having 1 to 12 C atoms, and aromatic hydrocarbons having 5 to 30 C atoms; x is an integer of 1 to 4, preferably 1 or 2; a, b, c, and d are integers; the sum a+b+c+d is at least x and not more than 12, preferably not more than 6, in particular not more than 4; a is at least 1, preferably 1 to 6, and preferably 1 or 2; b, c and d may be equal to 0, and are preferably each 0, 1 or 2. In this case, b is in particular 0 or 1 and c is preferably 0.

[0034] As is well known to those skilled in the art, the ratio of ligand to metal results from the oxidation state of the metal. In this case, the ligand L is of the formula R 1 -N3-R 2 [In the formula, R1 and R 2 is a hydrocarbon group having a single negative charge. Thus, for example, a metal in oxidation state II, such as Co(II) in formula (1), may be substituted with one or two ligands L.

[0035] Generally, it is preferred that the complex is as homogeneous as possible. In this case, the decay process is often less complicated, and as a result, there is less possibility of undesired side reactions occurring in the gas phase and coating reaction. In particular, it is preferred that the complex has only one or two different types of ligands, for example, only one type of ligand L and one type of X, or only two types of ligand L. The entire complex as ligand L is particularly preferably L 1 and L 2 In that case, c=0.

[0036] More preferably, the complex is L 1 In this case, b=0 and c=0. In a preferred embodiment, the complex has no ligand X, and therefore d=0. Again, embodiments where c=d=0 or b=c=d=0 are preferred. Such complexes have often been found to be particularly well behaved in vapor deposition processes, despite their low structural complexity.

[0037] In a preferred embodiment, the metal complex is homoleptic. In this case, the homoleptic complex has only one or more ligands L. The term "homoleptic" means that all ligands of the compound are identical. Homoleptic complexes are particularly preferred because their decomposition behavior in the gas phase is often more uniform and better controlled than heteroleptic metal complexes with different ligands. In accordance with the present invention, it has been found that homoleptic complexes have particularly good properties in terms of stability and volatility, which are required for vapor deposition. In particular, advantageous properties have been found for homoleptic complexes of In, Co, Cu, and La.

[0038] In another preferred embodiment, the metal complex is heteroleptic, meaning that the metal complex may have two or more different ligands, in particular two, three, or four different ligands. Thus, the metal complex of formula R 1 -N3-R 2 There may be two or more different ligands L of formula R 1 -N3-R 2 At least one ligand L and at least one other ligand must be present. In preferred embodiments, the heteroleptic metal complex comprises two or three different ligands. For example, heteroleptic ruthenium complexes are readily available and have been found to be suitable for deposition of Ru from the vapor phase in accordance with the present invention.

[0039] In a preferred embodiment, the metal complex has the formula R 1 -N3-R 2 The ligand L is only

[0040] In a further preferred embodiment, the metal complex further comprises additional ligands. In this case, preferably, there are no additional ligands that impair the advantageous properties in terms of stability and volatility, or that impair the deposition of pure metal from the gas phase. Therefore, preferably, there are no additional ligands with reactive elements, in particular selected from O, N, S, or P. Particularly preferably, there are no additional ligands with amine groups, such as tetramethylethylenediamine (TMEDA). In one embodiment, there are preferably no halogen-containing ligands. In a further preferred embodiment, there are no ligands with the structural elements NCN or N-aryl.

[0041] In a preferred embodiment, the metal complex comprises a metal atom and a compound of formula R 1 -N3-R 2 The metal complexes may also have two, three, four, or more metal atoms, with correspondingly more ligands present. The stoichiometry of such metal complexes is well known. 1 -N3-R 2The group is singly negatively charged.

[0042] R 1 Groups and R 2 The R groups are hydrocarbon groups, which means that they consist of the elements carbon and hydrogen. 1 and R 2 can generally be selected independently of each other.

[0043] In a preferred embodiment, R 1 =R 2 As a result, the overall compound may be particularly homogeneous, which may be advantageous in the deposition of metals from the gas phase, since the decomposition process is less complicated and side reactions are expected to be reduced.

[0044] In a preferred embodiment, R 1 and R 2 have, independently of one another, 1 to 25 C atoms, in particular 1 to 20 C atoms, in the context of the present application. In this case, R 1 and R 2 have, independently of one another, 1 to 15 C atoms, in particular 1 to 12 C atoms.

[0045] R 1 Groups and R 2 The groups may be independently selected from alkyl, alkenyl, aryl, and araryl. In one particular embodiment, R 1 and R 2 is an alkyl group. Preferably, the metal complex has a group of formula R 1 -N3-R 2 [In the formula, R 1 and R 2 At least one ligand L has an alkyl group. All ligands L, R of the metal complex 1 and R 2 Alkyl groups are preferred for the alkyl group. The alkyl group can be branched, cyclic or unbranched.

[0046] In the context of this application, the alkyl group R 1 and R 2may have, for example, 1 to 20 C atoms, particularly 1 to 15 C atoms, or 1 to 12 C atoms. The alkyl group is relatively short-chained and particularly preferably has 1 to 6 C atoms, particularly 1 to 4 C atoms.

[0047] In a preferred embodiment, R of the metal complex 1 Group and / or R 2 All or some of the groups are branched and / or cyclic alkyl groups. Preferred branched groups here are tert-butyl and isopropyl, especially tert-butyl. Preferred cyclic groups are bulky groups such as adamantyl or cycloalkyl, especially cyclohexyl.

[0048] R 1 and R 2 is particularly preferably selected from methyl, ethyl, propyl, isopropyl, tert-butyl, and n-propyl. 1 and R 2 is particularly preferably selected from methyl, ethyl, and tert-butyl. In a preferred embodiment, R 1 and R 2 is tert-butyl.

[0049] In a preferred embodiment, the metal complex has at least one ligand that is tert-butyl-N3-tert-butyl or tert-butyl-N3-methyl. In a preferred embodiment, the metal complex has only ligands that are tert-butyl-N3-tert-butyl and / or tert-butyl-N3-methyl. The metal complex is preferably homoleptic.

[0050] The metal complex may have an additional ligand X. The additional ligand X is preferably selected from halogen, H, CO, and hydrocarbon ligands. The hydrocarbon ligand is an alkyl group, especially having 1 to 12 carbon atoms, especially 1 to 4 carbon atoms, and particularly preferably 1 or 2 carbon atoms. Methyl is particularly preferred. Also preferred as the ligand X are aromatic hydrocarbons having 5 to 30 carbon atoms, especially 6 to 12 carbon atoms, such as pentene, benzene, or substituted benzenes, such as cymene or various di- or tri-alkylbenzenes. The aromatic group X may be neutral or negatively charged. Such aromatic ligands are known to be capable of stabilizing metal complexes, for example, complexes of Ru. The ligand may be an alkenyl ligand, especially having 1 to 12 carbon atoms. The halogen is preferably Cl.

[0051] The metal M may be any of the main group and minor group metals of the periodic table (excluding alkali metals). In accordance with the present invention, metal complexes may generally be used that may have a suitable bandwidth of the metal to deposit metals or metal compounds from the vapor phase.

[0052] It has been found that the use is particularly efficient when using metal complexes of metals from groups 8, 9 and 10 of the periodic table (especially Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), group 13 (Al, Ga, In, Tl), group 10 (Cu, Ag, Au), group 12 (especially Zn; or Cd or Hg), lanthanides (La, Ce, Pr, Nd, etc.) or actinides (Ac, Th, Pa, U, etc.). The metal in the complex preferably has the oxidation state 1, 2 or 3.

[0053] In a preferred embodiment, the metal M is selected from Co, Ru, Cu, Al, Ga, Tl, and La. Complexes of these metals with triazenide ligands can be obtained in a relatively simple manner using the method according to the invention. These metal complexes have been found to be highly suitable for deposition of the metal from the gas phase.

[0054] Particularly preferably used are metals selected from Al, In, Co, Cu and La. Metal complexes of these metals are particularly readily available and have been found to exhibit particularly advantageous properties in vapor deposition.

[0055] In a preferred embodiment, the metal M is selected from In, Co, Cu and Ru. In particular, there is a need in the prior art for precursor compounds for the deposition of such metals from the vapor phase.

[0056] In a preferred embodiment, the metal is M=Co. Co complexes have been found to be particularly sublimable, where the small molecule complexes can be evaporated at relatively low temperatures and substantially without residue.

[0057] In a preferred embodiment, the metal M=In. It has been found that the complexes are particularly easily sublimable or evaporable, allowing certain fractions to evaporate at relatively low temperatures. In a preferred embodiment, the In-complexes are liquid at 25° C. The compound In(dbt)Me2 (formula 9a, example 8) has been found to be liquid at 25° C. In-complexes that can be easily converted to the gas phase are particularly advantageous, since the prior art generally uses In-alkyl compounds such as trimethylindium, which are solid at room temperature and prone to uncontrolled, partially explosive, autocatalytic decomposition.

[0058] In a preferred embodiment, the metal is M=Ru. Such complexes are advantageous because only a few precursor compounds are available in the prior art that require improvement for converting and depositing Ru into the gas phase at relatively low temperatures. In a preferred embodiment, the Ru complex is liquid at 25° C. Thus, compounds of formulas (14) and (16) (Examples 14 and 16) were found to be liquid at 25° C., while other Ru complexes have very low melting points below 70° C. Liquid and solid Ru complexes that can be easily converted to the gas phase are particularly advantageous because no Ru compounds are available in the prior art that can be efficiently converted to the gas phase and used in such a manner.

[0059] In a preferred embodiment, the metal is M=Cu. The composition [Cu(R 1 -N3-R 2 )] n The Cu(I) complex of R 1 Group and / or R 2 Depending on the size of the group, dimers (n=2, R 1 =R 2 = tert-butyl), or tetramer (n = 4, R 1 = tert-butyl, R 2 The formation of such an association is typical of many metal compounds. Nevertheless, both compounds are very readily sublimable, allowing the low molecular weight complexes to evaporate into the gas phase at relatively low temperatures and virtually without residue.

[0060] In a preferred embodiment, the metal M = La. Such complexes are advantageous because only a few precursor compounds are available in the prior art that require improvement in order to convert lanthanum or other lanthanides with very high molecular weights into the gas phase at relatively low temperatures and deposit them.

[0061] In a preferred embodiment, the metal complex has the formula (2): M[(L 1 ) a X d ](2) [In the formula, L 1 is the formula R 1 -N3-R 2 (In the formula, R 1 and R 2 is an alkyl group having 1 to 12 C atoms, X is selected from H, halogen, CO and alkyl having 1 to 6 C atoms, a=2 or 3, d=0 or 1, M is selected from In, Co, Cu, Al, Ga, Tl, and La.

[0062] In a preferred embodiment, the metal complex is represented by formula (3) to (5): M[(L 1 )2X](3) [In the formula, L 1 is the formula R 1 -N3-R 2 (In the formula, R 1 and R 2 is an alkyl group having 1 to 12 C atoms, X is selected from H and alkyl of 1 to 6 C atoms, M=Al or Ga; M[(L 1 )3](4) [In the formula, L 1 is the formula R 1 -N3-R 2 (In the formula, R 1 and R 2 is an alkyl group having 1 to 12 C atoms, M=In, Tl or La; M x (L 1 ) a (5) [In the formula, L 1 is the formula R 1 -N3-R 2 (In the formula, R 1 and R 2 is an alkyl group having 1 to 12 C atoms, X is an integer from 1 to 4, a is an integer of 2 to 8, provided that a / x=1 or 2; M=Co or Cu. Here, in particular, when a / x=2, the metal is Co, and when a / x=1, the metal is Cu.

[0063] In a preferred embodiment, the metal complex has the formula (6): (Ru[(L 1 )X 1 X 2 ](6) [In the formula, L 1 is the formula R 1 -N3-R 2 (In the formula, R 1 and R 2 is an alkyl group having 1 to 12 C atoms, X 1 is an aromatic hydrocarbon ligand having 5 to 30 C atoms, X 2 is selected from any group other than H, halogen, CO and alkyl having 1 to 6 C atoms.

[0064] It has been found that the stability and volatility of Ru complexes may be lower than those of other metals. Regardless, elemental Ru can be separated from the gas phase along with the Ru complex. This is advantageous because there is a need in the art for Ru compounds suitable as precursor compounds for such methods. Ru complexes can be used, for example, to incorporate Ru as a doping metal, a liner metal, or a filler metal in materials for electronic applications.

[0065] In a preferred embodiment, the metal complex is a liquid at 25° C. and atmospheric pressure (1013 mbar). Liquids are particularly suitable for such a process because the transition to the gas phase already occurs at low temperatures and because liquids are particularly easy to handle. In a preferred embodiment, the metal complex is a solid at 25° C. and atmospheric pressure and has a relatively low evaporation temperature.

[0066] Preferably, the metal complex has a sublimation or evaporation temperature at atmospheric pressure of less than 120°C, especially less than 100°C.

[0067] Preferably, the transfer to the gas phase is carried out by evaporation or sublimation at a temperature below 120° C., in particular below 100° C. The evaporation or sublimation is preferably carried out at a temperature of 10° C. under reduced pressure. -3 in the range of 10 to 900 mbar, preferably 10 -2 ~1 mbar range, especially 10 -2 It is done in millibars.

[0068] Generally, the pressure in the process according to the invention is preferably set in the range customary for such processes. -3 in the range of 10 to 900 mbar, particularly preferably 10 -2 ~1 mbar range, especially 10 -2 In the context of the present application, the parameters of gas phase reactions, such as evaporation, sublimation or decomposition temperatures, or temperatures at which the compounds are stable, are preferably determined under reduced pressure in such reactions, especially at temperatures below 1000 K. -2 It is measured in millibars of pressure.

[0069] In a preferred embodiment, the metal complex is sublimable or vaporizable in the gas phase at atmospheric and / or reduced pressure without decomposition (decay). This means, for example, that up to 90%, up to 95%, or up to 98% by weight can be converted into the gas phase without decomposition. The decay can be followed by conventional methods, in particular by SDTA (Simultaneous Differential Thermal Analysis).

[0070] The metal complex is preferably thermally stable at atmospheric pressure, but is particularly thermally stable at 100°C, more preferably 120°C or 150°C under reduced pressure in the gas phase. This means that at such temperatures substantial decomposition does not yet occur, or at least 5% by weight or less, in particular 2% by weight or less, or 1% by weight or less, is decomposed. Preferably, the metal complex transitions to the gas phase below this temperature. The reduced pressure is 10 -3 in the range of 10 to 900 mbar, preferably 10 -2 ~1 mbar range, especially 10 -2 It is millibars.

[0071] In a preferred embodiment, metal complex has a relatively low molecular weight.Comparatively light complexes can often improve conversion to gas phase.The metal complexes described in the present application can advantageously be prepared using ligands with a relatively low molecular weight.The molecular weight of metal complex is preferably less than 600 g / mol, particularly preferably less than 450 g / mol, and very particularly preferably less than 350 g / mol.

[0072] The present invention also provides a method for producing a coated substrate, comprising the steps of: (a) providing a metal complex as described above; (b) depositing a metal or a compound of a metal onto the surface of the substrate by metal organic vapor deposition.

[0073] In a preferred embodiment, the method is metalorganic chemical vapor deposition (MOCVD). Metalorganic chemical vapor deposition (MOCVD, "metalorganic chemical vapor deposition") is a coating method from the class of chemical vapor deposition (CVD) methods, in which the deposition of a solid layer on a substrate occurs from the chemical vapor phase using organometallic precursor compounds (precursors).

[0074] In a preferred embodiment, the metal-organic vapor phase deposition method is metal-organic vapor phase epitaxy (MOVPE, "metal-organic vapor phase epitaxy", also called "organo-metallic vapor phase epitaxy", OMVPE). While any deposition on a substrate is possible using MOCVD, MOVPE is a growth method and therefore relates to growing crystals on crystalline substrates. This method, and in particular MOVPE, is used inter alia for the deposition of semiconductor materials.

[0075] The use and method according to the invention allow for the deposition of metals or metal compounds from the gas phase. The deposition is carried out on a substrate. Metal-containing deposits are generally called layers or coatings. The metal compounds are preferably selected from semiconductor compounds, alloys, nitrides, phosphides, arsenides, and silicides. Such compounds are obtained by known methods by adding further compounds in the gas phase that can react with the metal under the conditions of the system. For an overview, reference is also made to the above-mentioned publication by J. Zilko.

[0076] Metalorganic evaporation and metalorganic vapor phase deposition are preferably carried out as follows: The metal-containing layer is produced in a reaction chamber. The substrate to be coated is placed therein and heated to a high temperature. A gas flow, usually with a carrier gas and a metal complex as a precursor compound, is introduced into the reaction chamber, where the precursor compound in the gas phase is first decomposed, and free radical groups attach to the substrate. Thermally activated, the radical groups have a certain degree of freedom of movement on the substrate until the metal atoms are incorporated into the layer at suitable positions. As a result of the saturation of organic radicals with elemental hydrogen, volatile organic compounds are formed. This residual gas is evaporated from the reaction chamber. It is preferable to convert the metal complex into a gas phase before introducing it into the reaction chamber. In a less preferred embodiment, it is also conceivable that the liquid containing the metal complex only evaporates when it is introduced into the reaction chamber.

[0077] Surprisingly, it has been found that the metal complexes described in connection with the present application are highly suitable as precursor compounds for the deposition of metals from the gas phase. Surprisingly, they combine several advantageous properties required for such a process. They are very stable and volatile and can be used in such a way that practically no impurities are produced during the deposition of the metal or metal compounds on the substrate.

[0078] The metal complex preferably sublimes or vaporizes in the process without decomposition. During sublimation, a solid is initially introduced, whereas during evaporation, a liquid or solution is added. Therefore, preferably, there is no or substantial disintegration during the transformation of the metal complex into the gas phase. The disintegration process can be followed by conventional methods, in particular by SDTA (Simultaneous Differential Thermal Analysis).

[0079] The relevant properties of the metal complex as the temperature increases can be measured by thermogravimetric analysis (TGA), which can be carried out under normal pressure (1013 mbar) or reduced pressure. In this case, the curve volume / temperature (same T increase, for example, 5 or 10 K / min) preferably shows a neat profile. Sublimation generally occurs when a rapid weight loss occurs above the sublimation temperature, leaving no or very little residue in the process. Preferably, the TGA curve does not show any major defects such as unevenness.

[0080] The transfer of metal complex to the gas phase is preferably as complete as possible. In this case, in the case of TGA under atmospheric pressure and / or reduced pressure, it is preferable to leave as small a residue as possible, for example, less than 20 wt%, less than 10 wt%, less than 5 wt%, or particularly less than 3 wt%, based on the amount of metal complex used. The residue corresponds to a plateau value, at which the weight of the residue is estimated as T increases further, for example, up to 500 ° C, 600 ° C, or 700 ° C. If the weight of the residue is (significantly) lighter than the weight of the metal in the compound added, this indicates sublimation or evaporation of the compound. Preferably, during TGA, at least 50 wt%, particularly at least 80 wt%, or at least 90 wt% of the metal is converted into the gas phase. For reasons of efficiency, it is generally advantageous if the metal is quantitatively evaporated.

[0081] The metal complexes according to the present invention have been found to be relatively stable. They are preferably stable at room temperature, and therefore durable for a desired period of time. In a preferred embodiment, the metal complexes are thermally stable at temperatures up to 100°C.

[0082] In the case of TGA at atmospheric pressure, a 3% mass loss preferably occurs only at temperatures above 80° C., preferably above 100° C., particularly preferably above 120° C. A 3% mass loss preferably occurs at temperatures between 80° C. and 220° C., particularly between 80° C. and 160° C.

[0083] Preferably, the metal complex decomposes under the conditions of the deposition, which is usually carried out at a temperature of 100°C to 400°C, in particular 120°C to 300°C, or 150°C to 250°C, under reduced pressure. The complex is preferably in the gas phase at these temperatures. The reduced pressure is preferably 10 -3 in the range of 10 to 900 mbar, preferably 10 -2 ~1 mbar range, especially 10 -2 The decomposition is usually carried out exothermically. In this range, the decomposition is preferably complete.

[0084] The metal complex is preferably decomposed only after conversion to the gas phase. The decomposition should preferably be carried out at a temperature above the sublimation or evaporation temperature. Preferably, the decomposition temperature exceeds the sublimation or evaporation temperature by 200°C or less, 100°C or less, or preferably 50°C or less, especially under the above-mentioned reduced pressure. The metal complex is preferably completely decomposed or decomposed to 50% at this decomposition temperature. If the decomposition is carried out at a temperature not much higher than the sublimation or evaporation temperature, deposition in the gas phase can often be carried out with a certain efficiency.

[0085] A pure form of the elemental metal or desired compound of the metal is preferably obtained during deposition from the gas phase. This means that impurities are not measurable or are negligibly low, e.g., less than 500 ppb, less than 100 ppb, or less than 10 ppb. The purity of the deposited metal or metal-containing compound can be determined by conventional methods, such as secondary ion mass spectrometry.

[0086] In a further preferred embodiment, the coating contains at least one further atomic component, in particular at least one further metal or element selected from Si, N, P or As. Thus, according to known methods, it is possible to incorporate further metals or elements into the coating in order to obtain corresponding alloys or compounds.

[0087] The present invention also relates to a method for producing a metal complex according to the invention or a metal complex usable according to the invention, comprising the steps of: (A) Formula R1 -(N3)AR 2 providing a compound of formula (I) wherein A is selected from H or an alkali metal, in particular Li, Na or K, with Li being particularly preferred; (B) contacting with a compound of the metal.

[0088] Then, the formula R 1 -(N3)AR 2 The compound of reacts with a compound of the metal to form a metal complex. This reaction is preferably carried out in a single step. A is preferably an alkali, especially Li. The metal complex, especially R 1 Group, R 2 The groups and A are selected as described above.

[0089] The compound of the metal used in step (B) is preferably a metal salt, an organometallic compound, or another metal complex of the metal. The other metal complex preferably does not have a triazenide ligand, and in particular has the formula R 1 -N3-R 2 [In the formula, R 1 and R 2 is a hydrocarbon group].

[0090] In a preferred embodiment, the method for producing a metal complex comprises, before step (A), adding a compound R 1 -N3 and AR 2 From formula R 1 -(N3)AR 2 wherein A is an alkali metal. The entire process is preferably carried out in a single reaction mixture (as a "one-pot reaction").

[0091] The object of the present invention is also to provide compounds R 1 -N3 and AR 2 in a reaction mixture containing 1 -(N3)AR 2 wherein A is an alkali metal, preferably Li. 1 Group, R 2 The groups and A are selected as described above.

[0092] formula R 1 -(N3)AR 2 The preparation of the compound of formula (I) is preferably carried out in an inert solvent, especially a hydrocarbon such as pentane or hexane.

[0093] In one embodiment, the formula R 1 -(N3)AR 2 The compound is purified after the reaction by evaporating further components from the reaction mixture (Method A). When A is an alkali metal and in diethyl ether, the product precipitates as a solid and pure diethyl ether adduct (alkali salt) which can be separated by filtration (Method B). The diethyl ether adduct can be completely liberated from the ether under reduced pressure or, if desired, can be converted to the corresponding neutral compound (where A = H) by hydrolysis with water.

[0094] According to the present invention, the method according to the present invention comprises the steps of: preparing a metal complex and a compound of formula R, which is an essential intermediate for the synthesis of the complex; 1 -(N3)AR 2 It has now been found that compounds of formula R can be prepared efficiently and in high yields in a relatively simple manner. 1 -(N3)AR 2 A can also be a hydrogen radical H, in which case the compound as a whole is neutral. It has been found that the use of different metal salts leads to the efficient formation of metal complexes under relatively simple conditions. For example, metal complexes of Al, Ga, and In can be obtained from these compounds.

[0095] formula R 1 -(N3)AR 2 It has also been found that when the compound of formula (I) is an alkali metal salt, many metal complexes are available. In this case, A is in particular Li, Na or K, particularly preferably Li. Such compounds have been used according to the invention to prepare, for example, salts of Co, Cu or Ru in a simple manner and in high yields.

[0096] formula R 1 -(N3)AR 2 where A=H or an alkali metal, can be prepared by the precursor compound R 1 -N3 and AR 2

[0033] The reaction can be obtained in a simple manner by reacting 2-(2-methyl-2-phenylpropanol)-2-(2-methyl ...

[0097] In reaction with a metal complex, the compound of formula R thus obtained 1 -(N3)AR 2 A compound of formula (I), or the same compound from another source, is contacted with a compound of the metal with sufficient reactivity, for example, a metal salt or an organometallic compound of the metal, in particular a metal halide such as CoCl or CuCl, or an organometallic compound such as AlMe or InMe, or a metal hydride such as GaH(OEt), or a precursor metal complex such as La(HMDS) (HMDS = hexamethyldisilazane) or [RuCl(p-cymene)]. For example, in the case of cobalt, reaction with a simple salt is already sufficient, but organometallic precursor compounds have been found to be preferred for the main group III elements. Other metal complexes are preferably envisaged for converting ruthenium or lanthanum into the metal complexes according to the invention. In all cases, the reaction of the metal with formula R 1 -(N3)AR 2 It has been found that starting from the compound, stable complexes with the corresponding ligands can be obtained in high yields.

[0098] Without being bound by theory, it is believed that the relatively weak N-N single bond in the metal complex leads to relatively low-temperature, relatively uncomplicated thermal decomposition. Here, N is formed as a stable decomposition product, and nitrogen-containing alkyl groups are assumed to be formed as molecular volatile compounds. Because all reaction products are non-reactive or nearly non-reactive and safe to handle, this method can be carried out in a relatively simple manner and with high yields.

[0099] Also, R 1 or R 2 It is also advantageous that the ligand has a relatively low molecular weight, where Λ is, for example, methyl or tert-butyl. This results in relatively good vaporization or even sublimation properties at relatively low temperatures. The use of only these two ligands has been surprisingly found to be particularly important for providing highly volatile metal compounds for ALD and MOCVD. Synthesis via tert-butyl azide, which is readily available and, in particular, technically safe to handle, offers considerable advantages over established 1,3-diazaallyl systems such as N,N'-dialkylacetamide or N,N'-dialkyl-N"-dialkylguanidato ligand systems. Under ALD and CVD conditions, the decomposition temperatures of the triazenide complexes described below are lower, and undesired carbon incorporation is less pronounced than with amidinato and guanidinato complexes.

[0100] In step (B), it is preferred to use organometallic compounds, in particular organolithium compounds, in particular alkyllithiums having 1 to 6 carbon atoms, such as methyllithium. The compounds are preferably used in the form dissolved in ether. Pentane is preferably used as the solvent. Preferably, in step (B), the compounds of the metal are added to the compounds of step (A), in particular continuously, for example dropwise.

[0101] The present invention is particularly advantageous when ligand salts, especially lithium salts, are used as intermediates. The choice of solvent is crucial in the preparation of such organic salts. Thus, the lithium salt of methyl-tert-butyltriazine in pentane precipitates as a solvent when methyllithium dissolved in ether is used as the starting material. The lithium salt may be isolated by filtration, if desired. On the other hand, the lithium salt of di-tert-butyltriazine is soluble in pentane. After the reaction is complete, it can be isolated by evaporation of the clear reaction solution. In both syntheses, no by-products are obtained, and the yield is greater than 80%. If desired, the neutral ligand di-tert-butyltriazine can be easily obtained by aqueous workup of the reaction mixture.

[0102] The lithium salts can be thoroughly dried and further processed. They are soluble in non-polar solvents such as pentane or toluene, but also in other common solvents such as diethyl ether or THF. Therefore, they can be easily used in such solvents in subsequent reactions to prepare metal complexes. The corresponding neutral ligands, where A=H, which are distillable liquids, can also be used in all common solvents for subsequent reactions. Therefore, the method and intermediates according to the present invention enable the simple and efficient production of metal complexes in high yields.

[0103] formula R 1 -(N3)AR 2 Starting from this compound, various complex compounds can be obtained via the elimination pathways of salts, alkanes (especially methane), hydrogen, or amines. Two triazenide ligands can complex main group elements of groups III or V, such as gallium, indium, or antimony, in homoleptic or heteroleptic compounds. Complexes with transition elements (secondary group), such as Co, Cu, Ru, or La, can also be readily prepared.

[0104] For example, the simple preparation of intermediates and metal complexes, which can be carried out in a single reaction batch, does not produce problematic by-products, and therefore the process can be easily scaled up and carried out, for example, on an industrial scale. During conventional heating, metal complexes do not decompose in vapor deposition devices, particularly "bubbler" reservoirs, when heated to temperatures of, for example, 100°C. They then decompose, preferably at temperatures in the range of 100°C to 400°C, only after transition to the gas phase.

[0105] The present invention also relates to a compound of formula (1): M x [(L 1 ) a (L 2 ) b (L 3 ) c X d ](1) [In the formula, L 1 , L 2 and L 3 The ligand L is of the formula R 1 -N3-R 2 (In the formula, R 1 and R 2 are independently selected from the group At least L 1 Regarding R 1 Groups and R 2 The group is an alkyl group, X is independently selected from H, halogen, CO, and hydrocarbon ligands, in particular alkyl groups having 1 to 12 carbon atoms and aromatic hydrocarbons having 5 to 30 C atoms; x is an integer of 1 to 4, preferably 1 or 2; a, b, c, and d are integers; the sum a+b+c+d is at least x and not more than 12, preferably not more than 6, in particular not more than 4; a is at least 1, preferably 1 to 6, and preferably 1 or 2; b, c, and d may be equal to 0, and are preferably each 0, 1, or 2; The following conditions (i) to (ii): (i) M is selected from the metals and lanthanides of the VIIIth subgroup of the periodic table, in particular Ru, Co and La; (ii) at least one ligand L is tert-butyl; and at least one R 1 group or R 2 and wherein at least one of the following conditions is satisfied.

[0106] Generally, the metal complexes are those described in connection with this application for uses and methods. They therefore comprise, in particular, the metal, ligands, and groups, i.e., the M, L groups selected and described above. 1 , L 2 , L 3 , R 1 , R 2 , X, x, a, b, c, d. Preferred metal complexes are in particular those of the formula M(L 1 )2, M(L 1 )3, M2(L 1 )4 and M2(L 1 ) 6. Generally, x is preferably a number from 1 to 2, and a+b+c+d is preferably a number from 2 to 6.

[0107] In a preferred embodiment, the metal complex has one of the formulae (7) to (20), as well as (102) to (115): [ka] [ka] [ka] tert-Butyl-(N3)H-CH3 and formula R 1 -(N3)AR 2 [In the formula, R 1 and R 2 is an alkyl group and A is an alkali metal or alkaline earth metal, in particular Li, Na, Cs, Ca or K, particularly preferably Li, are also an object of the present invention.

[0108] In a preferred embodiment, the metal compound comprises one of formulas (21)-(23) or (116)-(117): [ka] R 1 Groups and R 2 The groups are selected as described above. Alkali metal compounds are important intermediates in the preparation of metal complexes. They can be prepared by the above-described simple methods and can be separated from the reaction mixture in a simple manner. The compounds are stable and can be converted into the corresponding neutral compounds (where A=H) by adding water. As a result, they are also in principle suitable for other chemical reactions and for the preparation of complexes for uses other than depositing metals from the gas phase.

[0109] The above-mentioned objectives are achieved by the use, method, and compound. New and improved compounds for separating metals from the gas phase are provided. The compounds have relatively high stability. In particular, compounds with high vapor pressures and simultaneously low decomposition points are provided. As a result, the compounds can be converted to the gas phase without substantial decomposition. In particular, the compounds have high stability and volatility at temperatures typically used for vapor deposition methods, particularly at temperatures between 100°C and 300°C. The compounds enable the deposition of various metals from the gas phase, and the metal-containing coatings are of high purity. The present invention also relates to a simple and efficient method for producing such compounds. The reagents used are readily available and safe to handle. The method can be carried out with high yields. The desired product is obtained in a few steps, or even as a one-pot process, and can be carried out under mild reaction conditions. [Brief explanation of the drawings]

[0110] [Figure 1]Figure 1 shows the thermogravimetric analysis (TGA) of the metal complexes prepared according to embodiment 6. The TGA curves show how the amount of metal complex used decreases with increasing temperature (% and mg / min and °C). In each case, the initial integral curve is also shown. Additionally, the starting amount (100%) and the plateau region of the remaining amount are shown, each of which is connected by a vertical line at 50% weight loss. [Figure 2] Figure 2 shows the thermogravimetric analysis (TGA) of the metal complexes prepared according to embodiment 7. The TGA curves show how the amount of metal complex used decreases with increasing temperature (% and mg / min and °C). In each case, the initial integral curve is also shown. Additionally, the starting amount (100%) and the plateau region of the remaining amount are shown, each of which is connected by a vertical line at 50% weight loss. [Figure 3] 3 shows the thermogravimetric analysis (TGA) of the metal complexes prepared according to embodiment 9. The TGA curves show how the amount of metal complex used decreases with increasing temperature (% and mg / min and °C). In each case, the initial integral curve is also shown. Additionally, the starting amount (100%) and the plateau region of the remaining amount are shown, each of which is connected by a vertical line at 50% weight loss. [Figure 4] 4 shows the thermogravimetric analysis (TGA) of the metal complexes prepared according to embodiment 10. The TGA curves show how the amount of metal complex used decreases with increasing temperature (% and mg / min and °C). In each case, the initial integral curve is also shown. Additionally, the starting amount (100%) and the plateau region of the remaining amount are shown, each of which is connected by a vertical line at 50% weight loss. [Figure 5]5 shows the thermogravimetric analysis (TGA) of the metal complexes prepared according to embodiment 11. The TGA curves show how the amount of metal complex used decreases with increasing temperature (% and mg / min and °C). In each case, the initial integral curve is also shown. Additionally, the starting amount (100%) and the plateau region of the remaining amount are shown, each of which is connected by a vertical line at 50% weight loss. [Figure 6] 6 shows the thermogravimetric analysis (TGA) of the metal complexes prepared according to embodiment 12. The TGA curves show how the amount of metal complex used decreases with increasing temperature (% and mg / min and °C). In each case, the initial integral curve is also shown. Additionally, the starting amount (100%) and the plateau region of the remaining amount are shown, each of which is connected by a vertical line at 50% weight loss. [Figure 7] 7 shows the thermogravimetric analysis (TGA) of the metal complexes prepared according to embodiment 13. The TGA curves show how the amount of metal complex used decreases with increasing temperature (% and mg / min and °C). In each case, the initial integral curve is also shown. Additionally, the starting amount (100%) and the plateau region of the remaining amount are shown, each of which is connected by a vertical line at 50% weight loss. [Figure 8] 8 shows the thermogravimetric analysis (TGA) of the metal complexes prepared according to embodiment 14. The TGA curves show how the amount of metal complex used decreases with increasing temperature (% and mg / min and °C). In each case, the initial integral curve is also shown. Additionally, the starting amount (100%) and the plateau region of the remaining amount are shown, each of which is connected by a vertical line at 50% weight loss. [Figure 9]9 shows the thermogravimetric analysis (TGA) of the metal complexes prepared according to embodiment 15. The TGA curves show how the amount of metal complex used decreases with increasing temperature (% and mg / min and °C). In each case, the initial integral curve is also shown. Additionally, the starting amount (100%) and the plateau region of the remaining amount are shown, each of which is connected by a vertical line at 50% weight loss. [Figure 10] 10 shows the thermogravimetric analysis (TGA) of the metal complexes prepared according to embodiment 17. The TGA curves show how the amount of metal complex used decreases with increasing temperature (% and mg / min and °C). In each case, the initial integral curve is also shown. Additionally, the starting amount (100%) and the plateau region of the remaining amount are shown, each of which is connected by a vertical line at 50% weight loss. [Figure 11] 11 shows the thermogravimetric analysis (TGA) of the metal complexes prepared according to embodiment 18. The TGA curves show how the amount of metal complex used decreases with increasing temperature (% and mg / min and °C). In each case, the initial integral curve is also shown. Additionally, the starting amount (100%) and the plateau region of the remaining amount are shown, each of which is connected by a vertical line at 50% weight loss. [Figure 12] 12 shows the thermogravimetric analysis (TGA) of the metal complexes prepared according to embodiment 19. The TGA curves show how the amount of metal complex used decreases with increasing temperature (% and mg / min and °C). In each case, the initial integral curve is also shown. Additionally, the starting amount (100%) and the plateau region of the remaining amount are shown, each of which is connected by a vertical line at 50% weight loss. [Figure 13]13 shows the thermogravimetric analysis (TGA) of the metal complexes prepared according to embodiment 20. The TGA curves show how the amount of metal complex used decreases with increasing temperature (% and mg / min and °C). In each case, the initial integral curve is also shown. Additionally, the starting amount (100%) and the plateau region of the remaining amount are shown, each of which is connected by a vertical line at 50% weight loss. [Figure 14] FIG. 14 is a graph showing the TGA and SDTA measurements of the compound of Example 16. [Figure 15] FIG. 15 is a graph showing the TGA and SDTA measurements of the compound of Example 22. [Figure 16] FIG. 16 is a graph showing the results of TGA and SDTA measurements of the compound of Example 24. [Figure 17] FIG. 17 is a graph showing the TGA and SDTA measurements of the compound of Example 25. [Figure 18] FIG. 18 is a graph showing the TGA and SDTA measurements of the compound of Example 26. [Figure 19] FIG. 19 is a graph showing the results of TGA and SDTA measurements of the compound of Example 32. [Figure 20] FIG. 20 is a graph showing the TGA and SDTA measurements of the compound of Example 33. [Figure 21] FIG. 21 is a graph showing the TGA and SDTA measurements of the compound of Example 34. [Figure 22] FIG. 22 is a graph showing the TGA and SDTA measurements of the compound of Example 35. [Figure 23] FIG. 23 is a graph showing the results of TGA and SDTA measurements of the compound of Example 36. [Figure 24] FIG. 24 is a graph showing the results of TGA and SDTA measurements of the compound of Example 37. [Example]

[0111] Illustrative Embodiments Summary of compounds produced: [ka] [ka] [ka]

[0112] Example 1: tert-butyl azide In general, organic azides are classified as explosive based on two criteria, both of which are experimental explosive limits. 1) [(Amount (N atom) + Amount (O atom)) / Amount (C atom)] <3 2) Weight percent of acidic nitrogen > 25 Ω%

[0113] According to both standards, the tert-butyl azide described herein should be classified as an explosive material. However, no accidents are known to have occurred during labeling or handling. Furthermore, it is a liquid that can be purified by distillation at 79°C, whereas the decomposition temperature of N2 is approximately 550°C, which is relatively high for an organic azide.

[0114] There are several synthetic approaches that have been reported since the late 1960s. For example, one approach starts with tert-butyl chloride, which is converted in CS with NaN and ZnCl as catalysts.

[34] Additionally, in another synthetic access, tert-butyl nitrate is converted with LiN3 in DMF. [35,36] Both approaches can lead to various problems due to incomplete reaction or incomplete separation of by-products. Furthermore, the use of carbon disulfide must be avoided due to its high toxicity. Therefore, a tert-butanol-initiated approach was investigated, in which the alcohol is reacted with NaN3 in a mixture of water and sulfuric acid.

[37] Literature indicates that scaling up the reaction to produce tert-butyl azide up to several hundred grams is possible and safe. Nevertheless, with this synthetic route, it is important to bear in mind that HN3 is formed in the reaction mixture and that it must be handled in a sufficiently dilute form.

[0115] 1.1 Synthesis of tert-butyl azide [ka] 75 mL of H2O and 50 mL of concentrated H2SO4 were added at -5 °C. NaN3 (9.80 g, 151 mmol, 1.10 equiv.) was slowly added using a solid dispenser. The colorless suspension was stirred for 15 minutes and warmed to 0 °C. tBuOH (10.2 g, 137 mmol, 1.00 equiv.) was slowly added dropwise via a dropping funnel. The solids present in the reaction mixture slowly dissolved during the process. The reaction solution was stirred at RT for 16 hours and transferred to a separatory funnel to achieve phase separation. The aqueous phase was separated and immediately neutralized with NaOH (2 m). The organic phase was washed twice with 20 mL of NaOH (2 m) each time and then dried over Na2SO4. The desired product was recondensed and obtained in the form of a colorless liquid in 69% yield (9.40 g, 94.8 mmol).

[0116] Example 2: Synthesis of H(dbt) and Li(dbt) 2.1 Synthesis of Li(dbt) - Method 1 [ka] tBuN3 (10.17 g, 102.6 mmol, 1.00 equiv.) was placed in 100 mL of pentane and cooled to 5 °C. Within 1 h, a solution of tBuLi (60 mL, 1.83 m, 110 mmol, 1.07 equiv.) in pentane was added dropwise. The dropping funnel was purged twice with 10 mL of pentane. The reaction mixture was slowly heated and stirred at RT for 1 h. 180 mL of HO was added to the slightly yellow suspension to decolorize the mixture. The aqueous phase was separated, and the organic phase was washed once more with 180 mL of HO. The organic phase was dried over Na2SO4, filtered, and the volatiles were removed in a FV. The crude product was purified by distillation at 60 mbar and 70 °C. The yield of the desired product, in the form of a clear, colorless liquid, was 32% (5.15 g, 32.7 mmol). [ka] H(dbt) (700 mg, 4.45 mmol, 1.00 equiv) was placed in 10 mL of EtO and cooled to 0 °C. A solution of nBuLi (1.8 mL, 2.5 m, 4.45 mmol, 1.00 equiv) in hexanes was added dropwise slowly. The slightly yellow solution was stirred at RT for 1 h, then brought to RT and stirred for an additional 24 h. The solvent of the clear solution was removed by vacuum evaporation to give a slightly yellow solid. The desired product was dried by vacuum evaporation and could be isolated in 95% yield (687 mg, 4.21 mmol).

[0117] 2.2 Synthesis of Li(dbt) - Method 2 (Optimized Synthesis) [ka] tBuN3 (1.27 g, 12.8 mmol, 1.00 equiv) was placed in 10 mL of pentane and cooled to 5 °C. A solution of tBuLi (7.4 mL, 1.83 m, 13.7 mmol, 1.07 equiv) in hexane was slowly added dropwise, resulting in a slightly yellow coloration of the reaction mixture. The reaction mixture was stirred at 5 °C for 1 h, then slowly warmed to RT and stirred for 1 h. The slightly cloudy solution was filtered through a syringe filter, and the solvent of the slightly yellow filtrate was removed by filtration. The desired product was obtained in 83% yield (1.64 g, 10.0 mmol).

[0118] No differences between the two batches of Li(dbt) could be observed in the analytical tests carried out. The optimized synthesis of Li(dbt) is a single-step synthesis without by-products. Although a neutral ligand was initially envisaged, the optimization leads to both savings in reagents and in various work steps such as distillation.

[0119] Example 3: Synthesis of K(dbt) [ka] BnK (700 mg, 4.45 mmol, 1.00 equiv.) was taken up in 10 mL of EtO and mixed with H(dbt) (582 mg, 4.47 mmol, 1.00 equiv.) dropwise at 0 °C. The colorless suspension was warmed to RT and stirred for 16 h. The slightly cloudy solution was filtered, and the solvent of the colorless filtrate was completely removed under reduced pressure. 85% (510 mg, 2.61 mmol) of the desired product was obtained in the form of a colorless solid.

[0120] Example 4: Synthesis of Li(mbt) [ka] tBuN3 (1.00 g, 10.7 mmol, 1.00 equiv.) was placed in 15 mL of pentane and cooled to 4 °C. A solution of MeLi in Et2O (6.8 mL, 1.60 m, 10.7 mmol, 1.07 equiv.) was slowly added dropwise to the reaction solution, yielding a colorless solid. The reaction mixture was warmed to RT, and the resulting colorless precipitate was filtered off and dried in a FV for several hours. The desired product was obtained as a colorless solid in 87% yield (1.13 g, 9.31 mmol). Scale-up of the reaction is possible.

[0121] Example 5: Synthesis of H(mbt) [ka] Li(mbt) (143 mg, 1.18 mmol, 1.00 equiv.) was placed in pentane and cooled to 0 °C. While stirring, FCCOOH (135 mg, 1.18 mmol, 1.00 equiv.) was slowly added dropwise, and slight effervescence of the reaction solution was observed. The Li(mbt) used went into solution upon warming the reaction mixture to RT, and the resulting slightly cloudy suspension was stirred at RT for 16 h. The suspension was filtered through a syringe filter, and after removing the pentane in a FV, the desired product was obtained in the form of a colorless liquid.

[0122] Example 6: Synthesis of [Al(dbt)2(Me)] [ka] A toluene solution of AlMe3 (33 mg, 0.46 mmol, 1.00 equiv.) was added dropwise to a mixture of H(dbt) (300 mg, 1.91 mmol, 3.00 equiv.) at RT. Gas evolution was immediately observed. The colorless reaction mixture was stirred at RT for 72 h and then filtered through a syringe filter. The solvent of the filtrate was removed by filtration to give a colorless oil. After repeated lyophilization, the desired product was obtained as a colorless solid (melting point: 46 °C) in 87% yield (276 mg, 0.56 mmol).

[0123] Thermogravimetric analysis of [Al(dbt)2(Me)] The crude product was analyzed by thermogravimetric analysis at 10 K / min up to 700 °C (Figure 1). The thermogravimetric analysis indicates a one-step process with an overall mass decomposition of approximately 91.2%. A 3% weight loss of the starting material was observed at 127.2 °C.

[0124] Example 7: Synthesis of [Ga(dbt)2(H)] [ka] A solution of GaCl3 (440 mg, 2.50 mmol, 1.00 equiv) in 5 mL of Et2O cooled to -78 °C was added dropwise to a suspension of LiH (260 mg, 32.8 mmol, 13.1 equiv) in 5 mL of Et2O. A slightly gray precipitate immediately formed. The reaction mixture was stirred at -78 °C for 2 h and then at RT for 16 h. The slightly gray suspension was filtered into a pre-cooled flask. To the clear filtrate was added dropwise at -78 °C a solution of GaCl3 (176 mg, 1.00 mmol, 0.40 equiv) in 5 mL of Et2O cooled to -78 °C. The suspension was heated to 0 °C with stirring and then filtered into a flask pre-cooled to -78 °C. The clear filtrate was added dropwise to a solution of H(dbt) (786 mg, 5.00 mmol, 2.00 equiv) in 5 mL of EtO at 0 °C. Gas evolution was immediately observed. The suspension was slowly warmed to RT and stirred for 16 h. The mixture was filtered through a syringe filter, and all volatiles were removed by FV. A colorless solid remained, which was taken up in 5 mL of hexane and filtered again through a syringe filter. The solvent of the filtrate was removed by FV to give the product in 53% yield (508 mg, 1.33 mmol, melting point: 46 °C). Single crystals for structural analysis could be obtained by sublimation at 60 °C by FV.

[0125] The corresponding dihydridogallium complex [Ga(dbt)H2] could not be obtained by a 1:1 conversion of H(dbt) with [GaH3(OEt2)].

[0126] Thermogravimetric analysis of [Ga(dbt)2(H)] The crude product was examined by thermogravimetric analysis at 10 K / min up to 900 °C (Figure 2). A total of 86.6% of the starting material was converted to the gas phase.

[0127] Example 8: Synthesis of [In(dbt)Me] [ka] H(dbt) (250 mg, 1.59 mmol, 1.00 equiv) was placed in 8 mL of pentane and cooled to 0 °C. A toluene solution of InMe3 (254 mg, 1.59 mmol, 1.00 equiv) was added dropwise, and slight gas evolution was observed. The reaction mixture was stirred at 0 °C for 1 h and at RT for 16 h. The solvent of the clear solution was removed in a FV, and the desired product was isolated as a colorless liquid. For purification, the product can be recondensed at 40 °C under a slight vacuum.

[0128] The reaction can also be carried out in a similar manner in toluene, but this makes isolation of the indium complex difficult due to the high volatility of the product.

[0129] Example 9: Synthesis of [In(dbt)3] [ka] InMe3 (150 mg, 0.94 mmol, 1.00 equiv.) was placed in 5 mL of toluene, cooled to 0 °C, and mixed with H(dbt) (444 mg, 2.83 mmol, 3.00 equiv.) and added dropwise. The reaction mixture was slowly warmed to RT and stirred for 16 h. The solvent of the clear solution was removed by freezing. The desired product was obtained in the form of a colorless solid in 73% yield (403 mg, 0.69 mmol). This could be sublimed by freezing at 80 °C.

[0130] Thermogravimetric analysis of [In(dbt)3] The crude product was examined by thermogravimetric analysis at 10 K / min up to 900 °C (Figure 3). The analysis indicates a one-step process with an overall mass decomposition of approximately 92.8%. A 3% weight loss of the starting material was observed at 196.7 °C.

[0131] Example 10: Synthesis of [La(dbt)3] [ka] [La(hmds)3] (225 mg, 0.36 mmol, 1.00 equiv) was placed in 10 mL of toluene and cooled to 0 °C. H(dbt) (171 mg, 1.09 mmol, 3.00 equiv) was added dropwise to the colorless solution. The clear, colorless reaction mixture was allowed to warm to RT and stirred for 16 h. 1 Using H NMR reaction control, it was confirmed that NO[La(hmds)3] was no longer present in the reaction mixture. All volatile components of the reaction solution were removed by freezing, and the resulting colorless solid was dried by freezing at 60 °C. The desired product was obtained in 72% yield (158 mg, 0.26 mmol).

[0132] Thermogravimetric analysis of [La(dbt)3] The crude product was examined by thermogravimetric analysis up to 800 °C at 10 K / min (Figure 4). Thermogravimetric analysis indicates a one-stage process with an overall mass decomposition of approximately 85%. At 85 °C, a weight loss of 3% of the starting material was observed. Up to 100 °C, it can be seen that residual traces of Hhmds are still present in the product. Starting at a temperature of 103 °C, an initial melting process of the lanthanum complex occurs, with the maximum mass loss achieved at a temperature of 250 °C. From a temperature of approximately 400 °C, no significant mass decomposition could be observed any more.

[0133] Example 11: Synthesis of [Co(dbt)2] [ka] Li(dbt) (654 mg, 4.00 mmol, 2.00 equiv.) was charged with CoCl (260 mg, 2.00 mmol, 1.00 equiv.) and blended with 15 mL of toluene. The reaction mixture was heated at 80 °C for 8 h, during which time a color change from blue to dark red was observed. The solvent of the cooled reaction mixture was removed in a FV, and the desired product was directly sublimed from the residue in a FV at 100 °C. [Co(dbt)] was obtained as a dark red, almost black solid in 53% yield (394 mg, 1.06 mmol).

[0134] Thermogravimetric analysis and residue determination of [Co(dbt)2] In the TGA curve (Figure 5) at 10 K / min up to 900 °C, a single mass loss step can be observed, with the maximum mass decomposition per hour observed at a temperature of 248 °C. At a temperature of 156 °C, the sample was decomposed to 3%. Starting at a temperature of 91 °C, an endothermic and very broad peak can be observed, which can be attributed to an irregular melting process. The total mass loss is 97%, and the residue obtained is examined in more detail by XRPD. The residue is found to be elemental cobalt.

[0135] Example 12: Synthesis of [Co2(mbt)4] [ka] Li(mbt) (193 mg, 1.59 mmol, 4.00 equiv.) and CoCl2 (103 mg, 0.79 mmol, 2.00 equiv.) were co-supplied and blended with 10 mL of toluene at 0 °C. Upon thawing, the reaction mixture exhibited a color change from blue to dark brown. The reaction mixture was heated at 80 °C for 10 h, and the solvent was removed at RT under vacuum. The desired product was sublimed from the dark brown residue at 85 °C under dynamic vacuum. The dinuclear cobalt complex was obtained as a reddish-brown solid in 51% yield (116 mg, 0.20 mmol). Single crystals for crystal structure analysis were obtained by mild vacuum sublimation at 100 °C. Due to the spin pairing of the two cobalt cores in [Co2(mbt)4], it exhibits diamagnetic behavior, in contrast to [Co(dbt)2].

[0136] Thermogravimetric analysis and residue determination of [Co2(mbt)4] The TGA curve of the cobalt complex at 10 K / min up to 900 °C (Figure 6) shows a one-stage process, with the maximum mass decomposition per hour observed at a temperature of 189 °C. A decomposition of 3% was measured at a temperature of 147 °C. Starting at a temperature of 184 °C, an initial exothermic process can be detected, which leads to the maximum mass decomposition per hour and can be attributed to the decomposition process. The total mass decomposition was 82%, and the residue obtained from this measurement was analyzed by XRPD. It could be identified as elemental cobalt.

[0137] Example 13: Synthesis of [Ru(dbt)(Cl)(p-cymene)] [ka] Li(dbt) (248 mg, 1.52 mmol, 1.00 equiv.) was placed in 5 mL of toluene. The ruthenium precursor (465 mg, 0.76 mmol, 0.50 equiv.) was added portionwise and rinsed with 4 mL of toluene. After a while, a color change from dark red to black was observed. The reaction mixture was stirred overnight at RT and filtered through a syringe filter. The solvent of the yellow-black filtrate was removed by FV. The desired product was obtained in the form of a dark green solid in 51% yield (331 mg, 0.77 mmol, melting point: 66.5 °C).

[0138] Thermogravimetric analysis of [Ru(dbt)(Cl)(p-cymene)] The TGA curve (Figure 7) at 5 K / min up to 600 °C shows a one-stage process with the maximum mass loss per hour at 235 °C. 3% decomposition occurs at a temperature of 153 °C, for a total mass decomposition of 67%. At a temperature of 67 °C, the melting process begins, proceeding almost continuously to a sublimation process. From a temperature of 200 °C, a further exothermic peak can be observed based on the SDTA curve, which can be attributed to a decomposition process (not shown). From a temperature of about 400 °C, the mass decomposition no longer changes significantly. Further examination of the residue obtained in the measurement by XRPD confirmed the presence of elemental ruthenium.

[0139] Example 14: Synthesis of [Ru(dbt)(H)(p-cymene)] [ka] [Ru(dbt)(Cl)(p-cymene)] (227 mg, 0.51 mmol, 1.00 equiv.) was added to 5 mL of toluene. At 0 °C, a solution of Li[HBEt3] (0.56 mL, 1 m, 0.56 mmol, 1.10 equiv.) in THF was added. The reaction mixture was slowly warmed to RT and stirred for 16 h. Precipitation of a colorless solid could be observed. The precipitated solid was separated by filtration, and the solvent of the filtrate was removed in a freezer. After repeated lyophilization, the desired product was obtained in the form of a green-black viscous liquid. For purification, the ruthenium hydride complex was recondensed in a freezer at 95 °C.

[0140] Alternatively, the synthesis can be carried out with LiAlH (0.25 equiv.). In contrast, the methyl-substituted complex, which can be represented by the exchange of [Ru(dbt)(Cl)(p-cymene)] and methyllithium, exists as a solid.

[0141] Thermogravimetric analysis of [Ru(dbt)(H)(p-cymene)] The crude product was examined by thermogravimetric analysis at 10 K / min up to 600 °C (Figure 8). The analysis indicates a one-step process with an overall mass decomposition of approximately 67.8%. A 3% weight loss of the starting material was observed at 150.5 °C.

[0142] Example 15: Synthesis of [Ru(mbt)(Cl)(p-cymene)] [ka] Li(mbt) (221 mg, 1.82 mmol, 1.00 equiv.) was placed in 10 mL of toluene and blended portionwise with [RuCl(p-cymene)] (559 mg, 0.91 mmol, 0.50 equiv.) at 0 °C. The mixture was slowly thawed to RT, and a color change from brown to dark green could be observed. The reaction mixture was stirred at RT for 16 h and filtered through a syringe filter. The solvent of the reddish filtrate was removed in a FV, and the remaining solid was lyophilized several times. The desired product was obtained in the form of a dark red solid in 59% yield (414 mg, 1.07 mmol, melting point: 51.9 °C).

[0143] Thermogravimetric analysis of [Ru(mbt)(Cl)(p-cymene)] The TGA / SDTA curve (Figure 9), measured at 5 K / min up to 700 °C, shows a single-stage mass decomposition with a maximum at a temperature of 169 °C. Above this temperature, the mass loss per time decreases again. This can be observed by itself based on the positive slope from the minimum. 3% decomposition of the ruthenium complex occurs at 118 °C. Starting at a temperature of 52 °C, an initial melting process is observed, which subsequently progresses to a sublimation process. The total mass loss is 64%. The residue obtained from this measurement was analyzed by XRPD analysis and could be identified as elemental ruthenium.

[0144] Example 16: Synthesis of [Ru(mbt)(H)(p-cymene)] [ka] [Ru(mbt)(Cl)(p-cymene)] (196 mg, 0.49 mmol, 1.00 equiv.) was dissolved in 5 mL of toluene and blended with a solution of Li[HBEt] (0.54 mL, 1 m, 0.54 mmol, 1.10 equiv.) in THF at 0 °C. The reaction mixture was slowly warmed to RT and stirred for 16 h, at which time a colorless solid precipitated. This was separated, and the solvent of the filtrate was removed by filtration. After repeated lyophilization, the desired product was obtained in the form of a black viscous liquid.

[0145] 1 H-NMR (C6D6, 300MHz, 300K): δ / ppm=-2.93(s, 1H, RuH), 1.21(d, 3 J HH =6.6Hz, 6H, CHMe2), 1.31(s, 9H, CMe3), 2.00(s, 3H, C arom .Me), 2.49(sept, 3 J HH =6.6Hz, 1H, CHMe2), 3.40(s, 3H, NMe), 4.72(d, 3JHH=4.6Hz, 2H, CH arom .), 4.91(d, 3 J HH =4.6Hz, 2H, CH arom .).

[0146]

number

[0147] TGA:(T S = 25℃, T E = 600 °C, 10 °C / min), Stage: 2 3% decomposition: 108.2℃, maximum decomposition (first stage): 181.3℃, maximum decomposition (second stage): 436.1℃, Mass resolution (first stage): 58.0%, total mass resolution: 64.8%.

[0148] SDTA:T D1(Onset) :97.3℃, T D1(max.) : 127.8℃, T D2(Onset) :162.1℃, T D2(max.) :169.8℃, T D3(Onset) :183.8℃, T D3(max.) :192.1℃.

[0149] FIG. 14 shows a graphical representation of the TGA and SDTA measurements.

[0150] Example 17: [Ru(mbt)(Cp * )(CO)] [ka] [RuCp * [Cl] (90 mg, 0.45 mmol, 1.00 equiv.) and Li(mbt) (216 mg, 1.79 mmol, 4.00 equiv.) were co-supplied and taken up in 25 mL of toluene. The dark brown solution was heated to 50 °C for 1 h and then cooled to RT. CO was passed through the reaction mixture at RT for 1 h. The dark red-black reaction solution was filtered through Celite®. The solvent was removed in a FV, leaving a dark red, almost black, honey-like solid, which was confirmed to be the desired product.

[0151] Thermogravimetric analysis of the crude product [Ru(mbt)(Cp*)(CO)] The crude product was analyzed by thermogravimetric analysis at 10 K / min up to 800 °C (Figure 10). In this case, a gradual decomposition can be observed with a total mass decomposition of 67%. The decomposition begins at a temperature of about 75 °C and is accompanied by an endothermic peak. A weight loss of 3% of the starting material was observed at 116.0 °C. The residue obtained from this run was analyzed by XRPD and could be identified as elemental ruthenium.

[0152] Example 18: Synthesis of [Ru(mbt)(Cp*)] [ka] [RuCp * [Cl] (100 mg, 0.50 mmol, 1.00 equiv.) and Li(mbt) (244 mg, 1.98 mmol, 4.00 equiv.) were co-supplied and taken up in 10 mL of toluene. The dark brown suspension was heated to 50 °C for 2 h and cooled to RT. The dark red-black reaction mixture was filtered through Celite®, and the filtrate's solvent was removed in a FV to isolate a dark green, almost black, honey-like solid.

[0153] Crude product [Ru(mbt)(Cp * )] thermogravimetric analysis The crude product was examined by thermogravimetric analysis at 10 K / min up to 800 °C (Figure 11). A gradual decomposition can be observed. The total mass loss is 57%. The decomposition begins at a temperature of about 79 °C, accompanied by an endothermic peak. A weight loss of 3% of the starting material was observed at 87.6 °C. The residue obtained from this run was analyzed by XRPD and could be identified as elemental ruthenium.

[0154] Example 19: Synthesis of [Cu2(dbt)2] [ka] Li(dbt) (280 mg, 1.72 mmol, 1.00 equiv.) was added along with CuCl (170 mg, 1.72 mmol, 1.00 equiv.) and blended with 10 mL of pre-chilled toluene. The reaction mixture was stirred at RT for 16 h, during which a color change from yellow to brown was observed. The suspension was filtered through Celite®, and the filtrate solvent was removed by FV. The crude product was purified by sublimation at 70 °C under dynamic vacuum to give a yellow solid in 71% yield (268 mg, 0.61 mmol). Single crystals for crystal structure analysis were obtained from a saturated solution in n-hexane at -21 °C.

[0155] thermogravimetric analysis The crude product was examined by thermogravimetric analysis at 10 K / min up to 1000 °C (Figure 12). [Cu2(dbt)2] showed a single mass loss step, with 3% decomposition at 156 °C. The total mass loss was 96%, which is attributed to the good sublimability of the copper compound. From temperatures above approximately 260 °C, no significant mass decomposition was observed. Elemental copper was observed as a residue in the crucible.

[0156] Example 20: Synthesis of [Cu4(mbt)4] [ka] Li(mbt) (208 mg, 1.72 mmol, 1.00 equiv.) and CuCl (170 mg, 1.72 mmol, 1.00 equiv.) were added and blended with 10 mL of pre-cooled toluene. The colorless reaction mixture was stirred at RT for 48 h, whereupon a color change to bright yellow could be observed. The suspension was filtered through Celite®, and the solvent of the filtrate was removed by FV. The bright yellow crude product was purified by sublimation under dynamic vacuum at 65-75 °C and obtained in 82% yield (248 mg, 0.35 mmol). Single crystals for crystal structure analysis could be obtained from a saturated solution in n-hexane at RT.

[0157] thermogravimetric analysis The crude product was examined by thermogravimetric analysis at 10 K / min up to 900 °C (Figure 13). [Cu4(mbt)4] showed a single-stage decomposition, with a total mass loss of 79%. 3% decomposition was at 198 °C, and the maximum mass decomposition was measured at approximately 250 °C. From a temperature of approximately 255 °C, no significant mass loss could be observed anymore. The SDTA curve shows various melting or phase transformation processes starting at a temperature of 236 °C until decomposition begins (not shown). The residue from the thermogravimetric analysis was examined by XRPD and could be identified as elemental copper.

[0158] Example 21: Synthesis of [Ca(dbt)2] [ka] Ca(hmds)2 (122 mg, 0.338 mmol, 1.00 equiv.) was placed in 10 mL of toluene and cooled to 0 °C. Hdbt (106 mg, 0.684 mmol, 2.00 equiv.) was added dropwise. The colorless reaction mixture was stirred at RT for 72 h, then filtered, and the filtrate was evaporated to dryness. The product was obtained as a light yellow solid in 63% yield (116 mg, 0.22 mmol).

[0159] 1 H-NMR (C6D6, 300MHz, 300K): δ / ppm=1.38(s, CMe3).

[0160] 13 C-NMR (C6D6, 75MHz, 300K): δ / ppm=31.1(CMe3), 56.2(CMe3).

[0161]

number

[0162] TGA:(T S = 25℃, T E = 800 °C, 10 °C / min), Stage: 1 3% decomposition: 115.3°C, maximum decomposition: 309.0°C, total mass decomposition: 79.3%.

[0163] SDTA:T D(Onset) : 194.4℃, T D(max.) :263.7℃.

[0164] RPD: Residue from TGA analysis: 2θ Lit.

[62] (2θ obs.) Ca3N2: 32.779 (32.785), 35.598 (35.545), 36.191 (36.175), 37.279 (37.375), 38.611 (38.455), 44.599 (44.755), 50.979 (50.665), 60.458 (60.415), 66.228 (66.265).

[0165] Example 22: Synthesis of [Si(dbt)4] [ka]

[0166] 1 H-NMR (C6D6, 300MHz, 300K): δ / ppm=1.30(s, CMe3).

[0167] 13 C-NMR (C6D6, 75MHz, 300K): δ / ppm=30.7(CMe3), 56.7(CMe3).

[0168]

number

[0169] Elemental analysis:C 32 H 72 N 12 For Si Calculated values: C: 58.85%, H: 11.11%, N: 25.74%. Actual values: C: 58.66%, H: 10.95%, N: 24.04%.

[0170] TGA:(T S = 25℃, T E = 900 °C, 10 °C / min), Stage: 1 3% decomposition: 184.3%°C, maximum decomposition: 261.3°C, total mass decomposition: 96.0%.

[0171] SDTA:T D1(Onset) :237.2℃, T D1(max.) :263.6℃.

[0172] FIG. 15 shows a graphical representation of the TGA and SDTA measurements.

[0173] μRFA: 97.6 wt% Si.

[0174] Example 23: Synthesis of [Sb(dbt)3] [ka] SbCl3 (92 mg, 0.403 mmol, 1.00 equiv.) was placed in 5 mL of n-hexane and cooled to -78 °C. A pre-cooled solution of [Li(dbt)] (197 mg, 1.21 mmol, 3.03 equiv.) in 5 mL of n-hexane was slowly added dropwise, causing the suspension to turn dark gray. The reaction mixture was stirred at -78 °C for 1 h and then at RT for 3 h. The dark gray suspension was filtered, and the filtrate was evaporated to dryness in a FV. The crude product was purified by sublimation at 90 °C in a FV. The product was isolated as a dark yellow solid in 43% yield (100 mg, 0.17 mmol).

[0175] HR-EI-MS:C 16 H 36 Calculated for N6: 433.2040 m / z, observed: 433.2037 m / z.

[0176] Melting point: 132°C (visual, 5°C / min).

[0177] 1H-NMR (C6D6, 300MHz, 300K): δ / ppm=1.39(s, CMe3).

[0178] 13C-NMR (C6D6, 75MHz, 300K): δ / ppm=30.6 (CMe3), 60.9 (CMe3).

[0179] IR: / cm -1 =2965(st), 2927(m), 2866(w), 1471(w), 1456(w), 1413(m), 1385(w), 1357(st), 1257(m), 1221(m), 1201 (st), 1144(vst), 1017(m), 930(w), 884(w), 802(w), 757(w), 618(st), 562(w), 499(m), 473(w), 431(w).

[0180] Elemental analysis:C 24 H 54 Against SbN9 Calculated values: C: 48.82%, H: 9.22%, N: 21.35%; Found values: C: 47.95%, H: 9.11%, N: 19.23%.

[0181] TGA:(T S = 25℃, T E = 700 °C, 10 °C / min), Stage: 1 3% decomposition: 150.6°C, maximum decomposition: 211.1°C, total mass decomposition: 92.8%.

[0182] SDTA:T D(Onset) :192.7℃, T D(max.) :209.4℃.

[0183] Example 24: Synthesis of [Sb(mbt)3] [ka] SbCl3 (250 mg, 1.10 mmol, 1.00 equiv.) and [Li(mbt)] (400 mg, 3.30 mmol, 3.00 equiv.) were added together and cooled to 0 °C. 10 mL of toluene pre-cooled to 0 °C was added while stirring. The yellow reaction mixture was stirred at RT for 20 h, and the solvent was removed by FV. After adding 10 mL of n-pentane, the suspension was filtered through Celite®, and the solvent of the slightly yellow filtrate was removed by FV. The crude product was obtained in 63% yield (320 mg, 0.69 mmol) and was quantitatively sublimed at 60 °C by FV. The product was in the form of a colorless solid.

[0184] 1 H-NMR (C6D6, 300MHz, 300K): δ / ppm=1.21 (s, 27H, CMe3), 3.27 (s, 9H, NMe).

[0185] 13 C-NMR (C6D6, 75MHz, 300K): δ / ppm=29.3(CMe3), 37.5(NMe), 59.1(CMe3).

[0186]

number

[0187] Elemental analysis:C 15 H 36 Against SbN9 Calculated values: C: 38.81%, H: 7.82%, N: 27.15%. Actual values: C: 37.25%, H: 7.55%, N: 26.62%.

[0188] EI-MS:C 10 H 24 Calculated for SbN6: 349.1101 m / z, Measured: 349.1005 m / z.

[0189] Melting point: 112°C (optically 5°C / min).

[0190] TGA:(T S = 25℃, T E = 900 °C, 10 °C / min), Stage: 1 3% decomposition: 134.4°C, maximum decomposition: 199.6°C, total mass decomposition: 96.1%.

[0191] SDTA:T M(Onset) :110.8℃, T M(max.): 116.3℃, T D(Onset) :187.2℃, T D(max.) : 202.6° C. Figure 16 shows a graphical representation of the TGA and SDTA measurements.

[0192] Example 25: Synthesis of [Bi(dbt)3] [ka] BiCl3 (103 mg, 0.33 mmol, 1.00 equiv) was placed in 10 mL of toluene and cooled to -16 °C. A solution of [Li(dbt)] (162 mg, 0.99 mmol, 3.00 equiv) in 5 mL of toluene was added dropwise. The brown reaction mixture was first warmed to RT and then stirred at 50 °C for 3 h. The solid was filtered off, and the red filtrate solvent was removed in a FV, leaving a red solid. The product was purified by sublimation in a FV at 60 °C as a red solid in 61% yield (136 mg, 0.20 mmol).

[0193] 1 H-NMR (C6D6, 300MHz, 300K): δ / ppm=1.32(s, CMe3).

[0194] 13 C-NMR (C6D6, 75MHz, 300K): δ / ppm=30.7(CMe3), 56.7(CMe3).

[0195] TGA:(T S = 25℃, T E = 900 °C, 10 °C / min), Stage: 1 3% decomposition: 126.6°C, maximum decomposition: 223.6°C, total mass decomposition: 57.3%.

[0196] SDTA:T D(Onset) : 102.6℃, T D(max.) : 153.4° C. Figure 17 shows a graphical representation of the TGA and SDTA measurements.

[0197] Example 26: Synthesis of [Bi(mbt)3] [ka] BiCl (175 mg, 0.56 mmol, 0.98 equiv.) was taken up in 5 mL of toluene, cooled to -70 °C, blended with [Li(mbt)] (207 mg, 1.71 mmol, 3.00 equiv.) and dissolved in 10 mL of toluene. The reaction mixture was slowly warmed to RT and stirred for 16 h, then heated to 50 °C for 4 h. The solvent of the green suspension was removed in a FV, and the product was sublimed from the residue at 65 °C as a yellow solid in 90% yield (277 mg, 50.2 mmol).

[0198] 1 H-NMR (C6D6, 300MHz, 300K): δ / ppm=1.20 (s, 27H, CMe3), 3.69 (s, 9H, NMe).

[0199] 13 C-NMR (C6D6, 75MHz, 300K): δ / ppm=29.7(CMe3), 42.6(NMe), 59.3(CMe3).

[0200]

number

[0201] EI-MS:C 10 H 24 Calculated for BiN6: 437.1866 m / z, Found: 437.1902 m / z.

[0202] Melting point: 105°C (visual, 5°C / min).

[0203] TGA:(T S = 25℃, T E = 900 °C, 10 °C / min), Stage: 1 3% decomposition: 152.4°C, maximum decomposition: 231.5°C, total mass decomposition: 81.9%.

[0204] SDTA:T M(Onset) : 106.9℃, T M(max.) : 109.5℃, T D(Onset) :233.4℃, T D(max.) : 243.4° C. Figure 18 shows a graphical representation of the TGA and SDTA measurements.

[0205] RPD: Residue from TGA analysis: 2θ of Bi Lit.

[63] (2θ obs. ):22.468(22.570), 23.794(23.620), 27.164(27.205), 37.955(37.975), 39.619(39.655), 44.554(44.575), 45.863(45.970), 46.020(46.030), 46.470(46.600), 48.700(48.700), 56.027(56.050), 59.325(59.290), 61.126(61.270), 62.181(62.185) , 62.895(62.815), 64.513(64.525), 67.439(67.510), 70.786(70.795), 71.528(71.515), 71.885(71.920), 73.711(73.750), 75.333(75.340), 76.408(76.330), 81.143(81.100), 85.000(84.970), 85.341(85.390), 87.089(87.085), 89.582(89.590).

[0206] Example 27: Synthesis of [Hg(mbt)2] [ka] [Li(mbt)] (200 mg, 1.65 mmol, 2.00 equiv.) was placed in 2 mL of THF and cooled to 0 °C. HgCl (224 mg, 0.83 mmol, 1.00 equiv.) was dissolved in 8 mL of THF and added dropwise. The reaction mixture was stirred at RT for 16 h. The slightly gray suspension was concentrated to dryness, taken up in n-pentane, and filtered through Celite®. After removing the solvent from the filtrate, the product was obtained as a slightly yellow viscous liquid in 12% yield (40 mg, 0.09 mmol).

[0207] 1 H-NMR (C6D6, 300MHz, 300K): δ / ppm=1.28 (m, 18H, CMe3), 3.31 (m, 6H, NMe).

[0208] 13 C-NMR (C6D6, 75MHz, 300K): δ / ppm=31.0(CMe3), 44.1(NMe), 57.8(CMe3).

[0209]

number

[0210] TGA:(T S = 25℃, T E = 600 °C, 10 °C / min), Stage: 2 3% decomposition: 127.1°C, maximum decomposition (first stage): 162.4°C, maximum decomposition (second stage): 358.4°C, mass decomposition (first stage): 68.1%, total mass decomposition: 100%.

[0211] SDTA:T D(Onset) : 143.0℃, T D(max.) :161.4℃.

[0212] Example 28: Synthesis of [Ce(dbt)3] [ka]

[0213] HR-EI-MS:C 24 H 54 Calculated for CeN9: 608.3557 m / z, Found: 608.3566 m / z.

[0214] Examples 29 and 30: Synthesis of [Zr(dbt)2(NMe2)2] and [Hf(dbt)2(NMe2)2] [ka] M(NMe2)4 (where M = Zr or Hf) was dissolved in 10 mL and / or 22 mL of Et2O, cooled to -78 °C, and blended with Hdbt dropwise. The reaction mixture was warmed to RT and stirred for 16 h. The solvent was then removed in a FV. The yellow residue was taken up in 10 mL of n-hexane, and the slightly cloudy solution was filtered. The solvent of the filtrate was removed under high vacuum, and the product was dried.

[0215] Example 29: [Zr(dbt)(NMe)] Yield: 91%.

[0216] 1 H-NMR (C6D6, 300MHz, 300K): δ / ppm=1.33 (s, 36H, CMe3), 3.05 (s, 12H, NMe2).

[0217] 13 C-NMR (C6D6, 75MHz, 300K): δ / ppm=30.2 (CMe3), 43.9 (NMe2), 57.5 (CMe3).

[0218] Elemental analysis:C 20 H 48 For ZrN8 Calculated values: C: 48.84%, H: 9.84%, N: 22.78%. Actual values: C: 48.41%, H: 9.77%, N: 23.23%.

[0219] Example 30: [Hf(dbt)(NMe)] Yield: 96%

[0220] 1 H-NMR (C6D6, 300MHz, 300K): δ / ppm=1.32 (s, 36H, CMe3), 3.15 (s, 12H, NMe2).

[0221] 13 C-NMR (C6D6, 75MHz, 300K): δ / ppm=30.2 (CMe3), 43.9 (NMe2), 58.6 (CMe3).

[0222] Elemental analysis:C 20 H 48 For HfN8 Calculated values: C: 41.48%, H: 8.35%, N: 19.35%. Actual values: C: 40.29%, H: 8.14%, N: 19.24%.

[0223] Example 31: Synthesis of Cs(dbt) [ka] Cshmds was taken up in 10 mL of Et2O and blended with Hdbt dropwise at 0°C. The slightly cloudy solution was warmed to RT, stirred for 16 h, and filtered through Celite®. The solvent of the filtrate was removed by FV. Yield: 76%.

[0224] 1 H-NMR (C6D6 / THF-d8(5 / 1), 300MHz, 300K): δ / ppm=1.35(s, CMe3).

[0225] 13 C-NMR (C6D6 / THF-d8(5 / 1), 75MHz, 300K): δ / ppm=31.3(CMe3), 55.8(CMe3).

[0226] Elemental analysis: C8H 18 For CsN3 Calculated values: C: 33.23%, H: 6.27%, N: 14.53%. Actual values: C: 32.60%, H: 6.07%, N: 14.64%.

[0227] Example 32: Synthesis of [Au2(dbt)2] [ka] AuCl (253 mg, 1.09 mmol, 1.00 equiv.) was suspended in 5 mL of THF, cooled to -75 °C, and blended with a solution of [Li(dbt)] (179 mg, 1.09 mmol, 1.00 equiv.) in 10 mL of THF. The reaction mixture was kept at -75 °C for 5 h, heated to RT, and stirred for an additional 16 h. The solvent of the brown reaction mixture was removed under high vacuum (FV), the residue was taken up in n-hexane, and the resulting suspension was filtered. The solvent of the filtrate was removed under high vacuum (FV), and the residue was purified by sublimation under high vacuum (FV) at 80 °C. The product was obtained in the form of a yellow solid in 13% yield (50 mg, 0.14 mmol).

[0228] 1 H-NMR (C6D6, 300MHz, 300K): δ / ppm=1.12 (s, 9H, CMe3), 1.27 (s, 18H, CMe3), 1.45 (s, 9H, CMe3).

[0229] 13 C-NMR (C6D6, 75MHz, 300K): δ / ppm=30.2(CMe3), 30.4(CMe3), 31.0(CMe3), 56.5(CMe3), 60.2(CMe3), 62.4(CMe3).

[0230]

number

[0231] Elemental analysis:C 16 H 36 For Au2N6 Calculated values: C: 27.20%, H: 5.14%, N: 11.90%; Found values: C: 29.77%, H: 5.75%, N: 13.46%.

[0232] HR-EI-MS:C 16 H 36 Calculated for Au2N6: 706.2333 m / z, found: 706.2324 m / z.

[0233] TGA:(T S = 25℃, T E = 900 °C, 10 °C / min), Stage: 1 3% decomposition: 121.8°C, maximum decomposition: 221.4°C, total mass decomposition: 62.0%.

[0234] SDTA:T D(Onset) :212.6℃, T D(max.) : 217.4° C. Figure 19 shows a graphical representation of the TGA and SDTA measurements.

[0235] Example 33: Synthesis of [Ag4(dbt)4] [ka] AgCl (250 mg, 1.70 mmol, 1.00 equiv.) was placed in 5 mL of THF and cooled to -70 °C. A solution of [Li(dbt)] (277 mg, 1.70 mmol, 1.00 equiv.) in 10 mL of THF was added. The deep brown reaction mixture was warmed to RT and stirred for 16 h, after which all volatile components were removed by FV. The residue was taken up in 10 mL of n-hexane, and the resulting thin reddish suspension was filtered. The solvent of the filtrate was removed by FV, and the residue was purified by sublimation at 90 °C by FV, affording the product as a colorless solid in 47% yield (178 mg, 0.20 mmol).

[0236] The reaction mixture and product should be handled in the absence of light.

[0237] 1 H-NMR (C6D6, 300MHz, 300K): δ / ppm=1.27(s, 36H, CMe3), 1.43(s, 36H, CMe3).

[0238] 13 C-NMR (C6D6, 75MHz, 300K): δ / ppm=31.0(CMe3), 31.9(CMe3).

[0239]

number

[0240] Elemental analysis:C 16 H 48 Ag4N 12 against Calculated values: C: 36.38%, H: 6.87%, N: 15.91%; Found values: C: 36.79%, H: 6.93%, N: 16.60%.

[0241] TGA:(T S = 25℃, T E = 700 °C, 10 °C / min), Stage: 1 3% decomposition: 205.4°C, maximum decomposition: 256.6°C, total mass decomposition: 78.7%.

[0242] SDTA:T D(Onset) :212.5℃, T D(max.) :215.2℃.

[0243] FIG. 20 shows a graphical representation of the TGA and SDTA measurements.

[0244] Example 34: Synthesis of [Ga(mbt)Me] [ka] GaMe3 (146 mg, 1.27 mmol, 2.00 equiv.) was placed in 5 mL of n-pentane and added at 0 °C to a solution of GaCl3 (112 mg, 0.64 mmol, 1.00 equiv.) in 10 mL of n-pentane. The colorless solution was warmed to RT, stirred for 16 h, recooled to 0 °C, and added to a solution of [Li(mbt)] (231 mg, 1.91 mmol, 3.00 equiv.) in 10 mL of n-pentane. The reaction mixture was warmed to RT and stirred for 16 h. The solvent of the suspension was removed in a FV, and the desired product was isolated from the residue by condensation in a FV. The product was obtained in the form of a colorless liquid in a yield of 57% (233 mg, 1.09 mmol).

[0245] 1 H-NMR (C6D6, 300MHz, 300K): δ / ppm=0.05 (s, 6H, GaMe2), 1.17 (s, 18H, CMe3), 3.03 (s, 3H, NMe).

[0246] 13 C-NMR (C6D6, 75MHz, 300K): δ / ppm=-5.6 (GaMe2), 29.7 (CMe3), 39.4 (NMe).

[0247]

number

[0248] TGA:(T S = 25℃, T E = 450 °C, 10 °C / min), Stage: 1 3% decomposition: 63.2°C, maximum decomposition: 100.9°C, total mass decomposition: 87.4%.

[0249] SDTA:T D(Onset) :81.6℃, T D(max.) :100.3℃.

[0250] FIG. 21 shows a graphical representation of the TGA and SDTA measurements.

[0251] Example 35: Synthesis of [Ga(dbt)Me] [ka] GaMe3 (181 mg, 1.58 mmol, 2.00 equiv.) was placed in 10 mL of n-pentane and added to a solution of GaCl3 (139 mg, 0.79 mmol, 1.00 equiv.) in 10 mL of n-pentane at 0 °C. The reaction mixture was warmed to RT and stirred for 16 h. At 0 °C, a solution of [Li(dbt)] (387 mg, 2.37 mmol, 3.00 equiv.) was added dropwise, and the precipitation of a colorless solid was immediately observed. The suspension was slowly warmed to RT and stirred for 16 h. The solvent was removed under high vacuum (FV), and the product was condensed from the residue in the form of a colorless liquid under FV. The product was obtained in a yield of 43% (261 mg, 1.02 mmol).

[0252] 1 H-NMR (C6D6, 300MHz, 300K): δ / ppm=0.10 (s, 6H, GaMe2), 1.17 (s, 18H, CMe3).

[0253] 13 C-NMR (C6D6, 75MHz, 300K): δ / ppm=-5.2 (GaMe2), 29.7 (CMe3), 55.8 (NMe).

[0254]

number

[0255] TGA:(T S = 25℃, T E = 450 °C, 10 °C / min), Stage: 1 3% decomposition: 64.2°C, maximum decomposition: 116.0°C, total mass decomposition: 89.9%.

[0256] SDTA:T D(Onset) :79.5℃, T D(max.) : 115.7℃

[0257] FIG. 22 shows a graphical representation of the TGA and SDTA measurements.

[0258] Example 36: Synthesis of [Al(mbt)3] [ka] A solution of AlCl3 (131 mg, 0.98 mmol, 1.00 equiv.) in 10 mL of Et2O was added dropwise to a solution of [Li(mbt)] (357 mg, 2.95 mmol, 3.00 equiv.) in 10 mL of Et2O at 0 °C. The colorless reaction mixture was slowly warmed to RT and stirred for 16 h before being filtered. The residue was extracted with 10 mL of Et2O, and the filtrate was evaporated to dryness in a FV. The pale yellow solid was sublimed under high vacuum at 45 °C to give the product in 21% yield (76 mg, 0.21 mmol).

[0259] 1 H-NMR (C6D6, 300MHz, 300K): δ / ppm=1.31 (s, 27H, CMe3), 3.16 (s, 9H, NMe).

[0260] 13 C-NMR (C6D6, 75MHz, 300K): δ / ppm=30.3(CMe3), 37.5(NMe), 55.8(CMe3).

[0261] 27 Al-NMR (C6D6, 130MHz, 300K): δ / ppm=28.1.

[0262]

number

[0263] Elemental analysis:C 15 H 36 For AlN9 Calculated values: C: 48.76%, H: 9.82%, N: 34.12%; Found values: C: 47.95%, H: 9.63%, N: 33.55%.

[0264] TGA:(T S = 25℃, T E = 700 °C, 10 °C / min), Stage: 1 3% decomposition: 124.6°C, maximum decomposition: 216.1°C, total mass decomposition: 96.4%.

[0265] SDTA:T M(Onset) :45.6℃, T M(max.) :49.7℃, T D(Onset) :205.1℃, T D(max.) :218.8℃

[0266] FIG. 23 shows a graphical representation of the TGA and SDTA measurements.

[0267] Example 37: Synthesis of [Al(dbt)3] [ka] [Al(NMe2)3]2 (154 mg, 0.97 mmol, 0.50 equiv) was placed in 10 mL of toluene, cooled to 0 °C, and blended with H(dbt) (458 mg, 2.91 mmol, 3.00 equiv) and added dropwise. The reaction solution was stirred at 0 °C for 1 h and then warmed to RT. Gas evolution was observed. The yellow solution was stirred at RT for 16 h, after which the solvent was removed in a freezer to give a pale yellow solid. The crude product was purified by sublimation in a freezer at 55 °C and isolated as a colorless solid in 51% yield (244 mg, 0.49 mmol).

[0268] 1 H-NMR (C6D6, 300MHz, 300K): δ / ppm=1.38(s, CMe3).

[0269] 13 C-NMR (C6D6, 75MHz, 300K): δ / ppm=31.2(CMe3), 57.2(CMe3).

[0270] 27 Al-NMR (C6D6, 130MHz, 300K): δ / ppm=24.6.

[0271]

number

[0272] Elemental analysis:C 24 H 54 Calculated for AlN9: C: 58.15%, H: 10.98%, N: 25.43%; Found: C: 58.25%, H: 10.13%, N: 24.32%.

[0273] TGA:(T S = 25℃, T E= 700 °C, 10 °C / min), Stage: 1 3% decomposition: 126.8 °C, maximum decomposition: 172.6, 302.0 °C, total mass decomposition: 95.3%.

[0274] SDTA: T D(Onset) : 270.0 °C, T D(max.) : 302.7 °C. Figure 24 shows the graphical representation of the TGA and SDTA measurements.

[0275] References [1] J.C. Brand, B.P. Roberts, J. Chem. Soc. Chem. Comm. 1981, 748 - 749. [2] R.H.J. Smith, C.J. Michejda, Synthesis 1983, 476 - 477. [3] R.H.J. Smith, B.D. Wladowski, A.F. Mehl, M.J. Cleveland, E.A. Rudrow, G.N. Chmurny, C.J. Michejda, J. Org. Chem. 1989, 54, 1036 - 1042. [4] D.H. Sieh, D.J. Wilbur, C.J. Michejda, J. Am. Chem. Soc. 1980, 3883 - 3887. [5] Soussi, K., Mishra, S, Jeanneau, E, Millet, J.-M., Daniele, S., Dalton Transactions 2017, 46, 38, 13055 to 13064 [6] C. Lego, B. Neumueller, Z. Anorg. Allg. Chem. 2011, 637, 1784 - 1789. [7] P. Gantzel, P.J. Walsh, Inorg. Chem. 1998, 37, 3450 - 3451. [8] D. Kalden, S. Krieck, H. Goerls, M. Westerhausen, Dalt. Trans. 2015, 44, 8089 - 8099. [9] H.S.Lee,S.-O.Hauber,D.Vindus,M.Niemeyer,Inorg.Chem.2008,47,4401-4412.

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Claims

1. The following general formula (1'): M ｘ [(L １ ) ａ X ｄ ] (1’) wherein M represents Ru and x is 1; L １ is the formula R １ -N ３ -R ２ (In the formula, R １ and R ２ each represents an alkyl group having 1 to 12 carbon atoms, and a is 1; X's each independently represent H, halogen, CO, or an aromatic hydrocarbon ligand; d is 1 or 2; When d is 1, X represents an aromatic hydrocarbon ligand; when d is 2, one of X represents an aromatic hydrocarbon ligand and the other X represents a group selected from H, halogen, and CO; The aromatic hydrocarbon ligand is selected from the group consisting of di- or tri-alkylbenzene and pentamethylcyclopentadienide ions. A Ru complex represented by the formula:

2. R １ and R ２ 2. The Ru complex according to claim 1, wherein each represents an alkyl group having 1 to 6 carbon atoms.

3. R １ and R ２ 2. The Ru complex according to claim 1, wherein each represents a methyl, ethyl, propyl, isopropyl, tert-butyl, or n-propyl group.

4. 2. The Ru complex according to claim 1, wherein the aromatic hydrocarbon ligand of X is p-cymene or a pentamethylcyclopentadienide ion.

5. 2. The Ru complex according to claim 1, wherein the aromatic hydrocarbon ligand of X is p-cymene or a pentamethylcyclopentadienide ion, and R 1 and R 2 each represent a methyl, ethyl, propyl, isopropyl, tert-butyl, or n-propyl group.

6. The following groups: 【Chemistry 1】 The Ru complex according to claim 1 , wherein the Ru complex is selected from the group consisting of:

7. 1. A method for producing a coated substrate, comprising: (a) preparing a Ru complex according to claim 1; (b) depositing Ru metal or a compound of Ru metal on the surface of the substrate by metalorganic vapor deposition of said Ru complex.

8. The method of claim 7, wherein the method is metal organic chemical vapor deposition (MOCVD).

9. The method of claim 7, wherein the method is metal organic vapor phase epitaxy (MOVPE).

10. The method according to any one of claims 7 to 9, wherein the Ru complex is sublimated or evaporated without decomposition.

11. The method according to any one of claims 7 to 9, wherein the Ru complex is decomposed in the gas phase at a temperature not exceeding its sublimation or evaporation temperature by 100°C or less.

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