Novel half-sandwich complexes of ruthenium

Abstract

Half-sandwich complexes of formulae η5-C5H5-nR1nRu(CO)2CmH2mNR2R3 and η5-C9H7-pR1 pRu(CO)2CmH2mNR2R3, wherein n = 0, 1, 2, 3, 4 or 5, m = 1, 2, 3, 4 or 5, p = 0, 1, 2, 3, 4, 5, 6 or 7, the radical(s) R1 are independently of one another selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals and the radicals R2 and R3 are independently of one another selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals.

Description

[0001] New half-sandwich complexes of ruthenium

[0002] The invention relates to novel ruthenium half-sandwich complexes, which, as ruthenium precursors, allow the deposition of thin ruthenium or ruthenium oxide layers on substrates using CVD or ALD (CVD = chemical vapor deposition; ALD = atomic layer deposition) processes. The novel half-sandwich complexes can also be used as homogeneous catalysts.

[0003] According to the common definition and also in the context of the present patent application, a CVD process is a process in which the vapor of a precursor is continuously fed from a heated reservoir under negative pressure conditions (0.1-10 mbar) into a reactor chamber, where it forms a layer on heated contact surfaces of a substrate, for example, contact surfaces of a semiconductor substrate, through thermal decomposition, for example, in the temperature range of 200 to 800°C. This continuous layer growth process can be supported by the addition of a co-reactant and / or by the inflow of an inert carrier gas such as nitrogen or argon.

[0004] According to the common definition and also in the context of the present patent application, an ALD process is a process in which the vapor of a precursor is pulsed sequentially and alternatingly with a co-reactant from a heated reservoir into a reactor chamber under negative pressure conditions (0.01-10 mbar). There, a layer is formed through self-limiting chemical reactions on the contact surfaces of a substrate, for example, contact surfaces of a semiconductor substrate, heated to a temperature in the range of >50 to 300 °C. Thus, layer growth during an ALD process does not occur continuously, but in cycles. The process can be supported during each pulse by the inflow of an inert carrier gas such as nitrogen or argon.

[0005] Ruchi Gaur, Lallan Mishra, M. Aslam Siddiqi and Burak Atakan provide an overview of ruthenium compounds suitable for the vapor deposition of ruthenium layers in RSC Adv., 2014, 4, 33785-33805.

[0006] WO 2009 / 015270 A1 discloses half-sandwich complexes of the formula Cp(R) n Ru(CO)2(X) with R = C1-C10 alkyl; X = C1-C10 alkyl; and n = 1, 2, 3, 4, or 5. WO 2009 / 015271 A1 discloses the use of such half-sandwich complexes for the deposition of a ruthenium film by ALD methods.

[0007] The object of the invention was to provide ruthenium compounds with improved properties for use in the production of ruthenium oxide layers or ruthenium layers using CVD or ALD processes, in particular for use in the production of ruthenium layers using CVD or ALD processes in the field of semiconductor production. The ruthenium compounds to be found should possess high volatility combined with thermal stability; in other words, they should be capable of being vaporized without decomposition at the lowest possible temperature, particularly in the range of 50 to 150°C.In the case of a CVD process, they should decompose into metallic ruthenium or lead to the formation of a ruthenium oxide layer through thermal treatment at temperatures above the boiling point, optionally using a co-reactant, or in the case of an ALD process, through reaction with a co-reactant at the typically prevailing process pressure. Upon decomposition to metallic ruthenium, they should be able to be deposited quickly in the form of layers as pure as possible, with as little or as little tolerable contamination from foreign atoms as possible, for example with a carbon, oxygen, or nitrogen content of <3 atomic percent each. In the field of semiconductor production, this means that the purest possible ruthenium metal layers should be deposited from the ruthenium compounds to be found on semiconductor contact surfaces using CVD or ALD processes.The ruthenium compounds to be found should also be liquid at room temperature, sufficiently stable towards air and water, not self-igniting, and as easy as possible to synthesize and purify.

[0008] The invention solves the problem by providing half-sandwich complexes selected from the group consisting of compounds of the formulas η 5 -C5H 5-n R1 n Ru(CO)2CmH 2m NR2R3 and η 5 -C9H7- P R1pRu(CO)2CmH2mNR2R3, where n = 0, 1, 2, 3, 4 or 5, preferably 0 or 1, in particular 0, m = 1, 2, 3, 4 or 5, p = 0, 1, 2, 3, 4, 5, 6 or 7, preferably 0 or 1, in particular 0, the radical(s) R1 are independently selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals, and the radicals R2 and R3 are independently selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals.

[0009] The term “isomeric butyl radicals” as used herein does not include isomeric butyl radicals with a cycloaliphatic structural unit.

[0010] Half-sandwich complexes selected from the group consisting of compounds of the formulas η 5 -C5H5-nR1nRu(CO)2C m H2mNR2R3, where n = 0, 1, 2, 3, 4 or 5, preferably 0 or 1, in particular 0, m = 1, 2, 3, 4 or 5, the radical(s) R1 are independently selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals, and the radicals R2 and R3 are independently selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals. Particularly preferred half-sandwich complexes are those of the formulas η 5 -C5H5Ru(CO)2C m H2mNR2R3, where m = 1, 2, 3, 4 or 5, and the radicals R2 and R3 are independently selected from methyl and ethyl. Especially preferred are η 5 -C5H5Ru(O)2C3H6N(CH3)2and η5 -C5H5Ru(CO)2C3H6N(CH2CH3)2, more precisely η 5 -C5H5Ru(CO)2(CH2)3N(CH3)2, i.e. dicarbonyl(η 5 -cyclopentadienyl)(3-dimethylaminopropyl)ruthenium and η 5 -C5H5Ru( O)2(CH2)3N(CH2OH3)2, i.e. dicarbonyl(η 5 - cyclopentadienyl)(3-diethylaminopropyl)ruthenium.

[0011] The half-sandwich complexes of the invention can form dimers or oligomers. This process can be reversible.

[0012] The invention also relates to processes for producing the half-sandwich complexes according to the invention.

[0013] A first process for the preparation of a half-sandwich complex according to the invention selected from the group consisting of compounds of the formulas η 5 -O5H5-nR1 nRu(CO)2C m H2mNR2R3 and η 5 -C9H7- P R1 pRu(CO)2C m H2mNR2R3 includes or consists in the implementation of η 5 -C5H5- n R1 n Ru(CO)2Hal or η 5-C9H7-pR1 pRu(CO)2Hal with an organometallic compound of type MC m H 2m NR2R3 or of the type Zn(C m H2mNR2R3)2or with a Grignard compound of the type Mg(C m H 2m NR2R3)X, where n = 0, 1, 2, 3, 4 or 5, preferably 0 or 1, in particular 0, m = 1, 2, 3, 4 or 5, p = 0, 1, 2, 3, 4, 5, 6 or 7, preferably 0 or 1, in particular 0, the radical(s) R1 are independently selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals, the radicals R2 and R3 are independently selected from methyl, ethyl, propyl,

[0014] Isopropyl and the isomeric butyl residues,

[0015] Hal = CI, Br or I, preferably CI means

[0016] M = Li, Na or K, and

[0017] X = CI or Br.

[0018] The procedure includes the following steps:

[0019] (A1 ) Provision of η5 -C5H5. n R1 nRu(CO)2Hal or η 5 -C9H7-pR1 P Ru(CO)2Hal and an organometallic compound of type MC m H2mNR2R3 or of the type Zn(C m H2mNR2R3)2or a Grignard compound of the type Mg(C m H2mNR2R3)X, and

[0020] (A2) Implementation of the η provided in step (A1 ) 5 -C5H5- n R1 n Ru(CO)2Hal or η 5 -C9H7-pR1 pRu(CO)2Hal with the MC also provided in step (A1) m H2mNR2R3 or Zn(C m H2mNR2R3)2or Mg(C m H2mNR2R3)X to form η 5 -C5H5-nR1 nRu(CO)2C m H2mNR2R3 respectively of η 5 -C9H7- P R1 pRu(CO)2C m H2mNR2R3.

[0021] The reaction taking place in step (A2) can be illustrated by the formation of η 5 -C5H5-nR1 nRu(CO)2C m H2mNR2R3 can be represented as follows: η 5 -C5H5.nR1 nRu(CO)2Hal + MCm H2mNR2R3 η 5 -C5H5-nR1 nRu(CO)2C m H2mNR2R3 + MHal or

[0022] 2 n 5 -C5H5.nR1 nRu(CO)2Hal + Zn(CmH2mNR2R3)22 η 5 -C5H5. n R1 nRu(CO)2C m H 2m NR2R3 + ZnHab or η 5 -C5H5. n R1 n Ru(CO)2Hal + Mg(C m H2mNR2R3)X, -> η 5 -C5H5. n R1 nRu(CO)2C m H2mNR2R3 + Mg(Hal)X.

[0023] The starting compound η mentioned in the three reaction equations above 5 -C5H5- n R1 nRu(CO)2Hal can be prepared according to or analogously to RJ Kulawiec, JW Faller and RH Crabtree, Organometallics 1990, 9, 745, or S. Dev, JP Selegue, J. Organomet. Chem. 1994, 469, 107. The preparation procedure for η 5 -C5H5- n R1 nRu(CO)2Hal involves the reaction of the commercially available tricarbonyldichlororuthenium(II) with η 5 -C5H5- n R1 nTI or with η 5 -C5H5- n R1 n Si(CH3)3. The production of organometallic starting materials of type MC m H2mNR2R3, Mg(C m H2mNR2R3)X or Zn(C m H2mNR2R3)2 requires no further explanation and is part of the standard knowledge of the person skilled in the art, i.e. a chemist. The HalC required in this context m H2mNR2R3 can be prepared from the corresponding commercially available hydrochloride HalC m H2mN + HR2R3CI' can be prepared by reaction with a base such as KOH (see Example 2 explained below).

[0024] Needless to say, it is advisable for those skilled in the art to work under the substantial exclusion of water and oxygen during steps (A1) and especially (A2). Step (A2) is conveniently carried out in an aprotic solvent. Suitable reaction temperatures are, for example, in the range of 10 to 70°C.

[0025] Preferred embodiments of the first process consist, according to the above, in corresponding processes for producing a half-sandwich complex according to the invention selected from the group consisting of compounds of the formulas η 5 -C5H 5-n R1 n Ru(CO)2C m H2 m NR2R3, especially with n = 0, especially η 5 -C5H5Ru(CO)2(CH2)3N(CH3)2 respectively η 5 -C5H5Ru(CO)2(CH2)3N(CH2CH3)2.

[0026] A second and preferred process for preparing a half-sandwich complex according to the invention selected from the group consisting of compounds of the formulas η 5 -C5H5-nR1 nRu(CO)2C m H2mNR2R3 and η 5 -C9Hz.pR1 pRu(CO)2C m H2mNR2R3 includes or consists in the conversion of the dimer [η 5 -C5H 5-n R1 n Ru(CO)2]2 or the dimer [η 5 -C9H7.pR1 pRu(CO)2]2 with HalCmH2mNR2R3 in the presence of a reducing agent Y, where n = 0, 1, 2, 3, 4 or 5, preferably 0 or 1, in particular 0, m = 1, 2, 3, 4 or 5, p = 0, 1, 2, 3, 4, 5, 6 or 7, preferably 0 or 1, in particular 0, the radical(s) R1 are independently selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals, the radicals R2 and R3 are independently selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals, Hal = Cl, Br or I, preferably Cl, and

[0027] Y is selected from Li, Na, K, Mg, Ca, Zn, H2, hydrazine, NaK alloy, NaH, lithium naphthalide, sodium naphthalide, potassium naphthalide, NaBH4, and LiAlH4. The process comprises the following steps:

[0028] (B1 ) Provision of [η 5 -C5H 5-n R1nRu(CO)2]2 or [η 5 -C9H7-pR1 P Ru(CO)2]2, from HalC m H2mNR2R3 and of Y, and

[0029] (B2) Implementation of the [η 5 -C5H5-nR1 nRu(CO)2]2 or [η 5 -C9H7-pR1 pRu(CO)2]2 with the HalC also provided in step (B1) m H2mNR2R3 in the presence of Y also provided in step (B1 ) to form η 5 -C5H5- n R1 nRu(CO)2C m H2mNR2R3 respectively of η 5 -C9H7-pR1 pRu(CO)2C m H2mNR2R3.

[0030] The reducing agent Y reduces the carbon atom directly bound to Hal.

[0031] The reaction can be illustrated by the formation of η 5 -C5H5-nR1 nRu(CO)2CmH2mNR2R3 using sodium as reducing agent Y as follows: [η 5 -C5H 5.n R1 n Ru(CO)2]2 + 2 HalC m H2mNR2R3 + 2 Na 2 NaHal +

[0032] 2 n 5 -C5H 5.n R1 n Ru(CO)2C m H2mNR2R3.

[0033] Using the example of the formation of η 5 -C5H5-nR1nRu(CO)2C m H2mNR2R3 using sodium naphthalide as reducing agent Y, the reaction can be represented as follows: [η 5 -C5H5- n R1 n Ru(CO)2]2 + 2 HalC m H2mNR2R3 + 2 C 10 H8Na 2 NaHal + 2 CwHs + 2 η 5 -C5H 5-n R1 n Ru(CO)2C m H2mNR2R3.

[0034] The starting compound [η 5 - C5H5-nR1 n Ru(CO)2]2 can be prepared according to or analogously to Kai F. Kalz, Nicole Kindermann, Sheng-Qi Xiang, Andreas Kronz, Adam Lange and Franc Meyer, Organometallics, 2014, 33, 1475-1479.

[0035] Regarding the production of HalC m The above applies to H2mNR2R3.

[0036] It goes without saying for the person skilled in the art that it is expedient to work with the greatest possible exclusion of water and oxygen during steps (B1) and in particular (B2). Step (B2) is expediently carried out in an aprotic solvent. Depending on the reducing agent Y selected, suitable reaction temperatures are, for example, in the range from -78 to 70°C. Preferred embodiments of the second process, according to the above, consist of corresponding processes for preparing a half-sandwich complex according to the invention selected from the group consisting of compounds of the formulas η 5 -C5H5-nR1 nRu(CO)2C m H2mNR2R3, especially with n = 0, especially η 5 -C5H5Ru(CO)2(CH2)3N(CH3)2 respectively η 5 -C5H5Ru(CO)2(CH2)3N(CH2CH3)2.

[0037] The half-sandwich complexes according to the invention fulfill the object explained above. They can be used as homogeneous catalysts. In particular, they are outstandingly suitable as precursors for the production of ruthenium layers or ruthenium oxide layers on substrates by means of CVD or ALD processes, in particular of ruthenium layers in the field of semiconductor production, i.e. in particular for the production of ruthenium layers on contact surfaces of semiconductor substrates. They are vaporizable at atmospheric pressure in the temperature range from 50 to 150°C, or more precisely, vaporizable without decomposition. The half-sandwich complexes η according to the invention are particularly suitable for the deposition of a high-purity ruthenium layer on contact surfaces of semiconductor substrates by means of CVD or ALD processes. 5 -C5H5Ru(CO)2(CH2)3N(CH3)2and η 5 -C5H5Ru(CO)2(CH2)3N(CH2CH3)2.

[0038] The half-sandwich complexes according to the invention are superior to the compounds known from WO 2009 / 015270 A1 which do not have dialkylamino substituents with regard to the task explained at the outset, as a comparison of the half-sandwich complexes according to the invention η 5 -C5H5Ru(CO)2(CH2)3N(CH3)2and η 5 -C5H5Ru(CO)2(CH2)3N(CH2CH3)2with the compound η described in WO 2009 / 015270 A1 5 -C5H5Ru(CO)2(CH2CH3). The thermogravimetric analysis of the compounds (see Figure 5) shows that the half-sandwich complexes according to the invention as well as η 5-C5H5Ru(CO)2(CH2CH3) in the particularly preferred temperature range of 50 to 150°C (beginning of the decline of the curves). The mathematical derivations of the functions obtained from the thermogravimetric analysis for the compounds investigated (cf. Figure 6) clearly show a single minimum for the half-sandwich complexes according to the invention and thus only one thermal event, which can be attributed exclusively to the evaporation process. In contrast, for η 5 -C5H5Ru(CO)2(CH2CH3) two closely spaced minima can be observed in the curve, thus indicating two thermal events. These represent the evaporation process on the one hand, but also an additional decomposition event on the other.

[0039] Thus, the half-sandwich complexes according to the invention completely fulfill the task explained at the beginning and in comparison to the non-evaporable compound η 5-C5H5Ru(CO)2(CH2CH3) in a superior manner. Such a decomposition process of a ruthenium precursor during evaporation can usually lead to inferior quality layers in the production of ruthenium layers or ruthenium oxide layers by vapor deposition. Due to the decomposition, not only evaporated precursor molecules are present in the gas space, but also decomposition products of the precursor, which no longer follow the same deposition mechanism as the actual precursor molecules and can thus increase the proportion of foreign atoms in the built-up layers. In addition, the half-sandwich complexes according to the invention can ensure a more stable process for the production of ruthenium layers or ruthenium oxide layers by vapor deposition. While the compound η 5-C5H5Ru(CO)2(CH2CH3) decomposes when heated above the boiling point and thus the material changes its composition over time, the composition of the half-sandwich complexes according to the invention remains constant over time. Therefore, the process parameters selected at the beginning of the deposition process are compatible with the inventive

[0040] Half-sandwich complexes are effective over a long period of time without adjustment, whereas the process parameters for the compound η 5 -C5H5Ru(CO)2(CH2CH3) may require adjustment during the deposition process.

[0041] Examples

[0042] All reactions and handling of air- and moisture-sensitive compounds were performed under a dry argon atmosphere (Air Liquide, 99.995%) using conventional Schlenk techniques. All solvents were dried (MBraun Solvent Purification System) and stored over molecular sieves (4 Å) under an argon atmosphere. All vacuum operations (e.g., solvent removal, sublimation, vacuum distillation) were performed at a pressure of 10' 1 up to 10' 2 mbar. Sample preparation for analytical purposes was performed in a glove box under argon atmosphere. All commercially available chemicals were used without further purification.

[0043] Analyses of the elements C, H, and N were performed using a Vario Mikro Cube CHNS analyzer from Elementar. The Ru content was determined after microwave digestion using an ICP-OES from Spectra, Spectra Acros. The oxygen content was calculated by summing the measured values ​​for C, H, N, and Ru and subtracting them to 100. A Bruker Avance III 400 NMR spectrometer was used for NMR characterization. All spectra were referenced using the internal solvent signal (C6D5H) and analyzed using the MestReNova v.10.0.2-15465 software from Mestrelab Research SL.

[0044] The IR spectrum was measured on a PerkinElmer FT-IR spectrometer Two with a PerkinElmer UATR Two ATR unit in an argon-flushed glove box.

[0045] Thermogravimetric analyses were performed on a Netzsch STA 409 PC LUXX in an argon-flushed glove box at atmospheric pressure (sample size approximately 10 mg) with a heating rate of 5 K / min (N2, flow rate = 300 mL / min).

[0046] The isothermal thermogravimetric analysis was performed on a Netzsch STA 409 PC LUXX at a N2 gas flow of 90 sccm in an argon-flushed glove box. Sample weights for all three isotherms were approximately 14 mg. After reaching the isothermal temperature (heating rate 10 K / min), the temperature was kept constant. Evaporation rates were derived from the slope of the linear regression. The crucible area was 0.29706 cm². 2 with a crucible diameter of 0.615 cm.

[0047] Example 1 (Preparation of the reducing agent sodium naphthalide):

[0048] 1.6 g of naphthalene was dissolved in 50 ml of tetrahydrofuran (THF), and 288 mg of freshly cut sodium hydroxide pieces were added to this solution at room temperature. The mixture was stirred at room temperature for 20 hours and subsequently used without further workup.

[0049] Example 2 (Preparation of N,N-Dimethylaminopropyl chloride): N,N-Dimethylaminopropyl chloride hydrochloride [CI(CH2)3N + H(CH3)2Cl] was mixed with 1.9 equiv. of KOH (technical grade powder) while cooling in an ice bath and stirred overnight. The resulting colorless oil was distilled in vacuo to a further 1.9 equiv. of KOH (technical grade pellets) (distillation receiver cooled with liquid N2). The resulting distillate was distilled a second time in vacuo (distillation receiver cooled with liquid N2), and the resulting oil was used without further workup.

[0050] Example 3 (Alternatives 3a and 3b): Inventive Example 3a (Preparation of Dicarbonyl(η 5 -cyclopentadienyl)(3-dimethylaminopropyl)ruthenium fη 5 -C5H5Ru(CO)2(CH2)3N(CH3)2 respectively η 5 - CsHsRufCOkDMPI with sodium naphthalide):

[0051] A Schlenk tube was charged with a solution of 1.0 g of [rp-CsHsRutCO^h] (prepared according to Kai F. Kalz, Nicole Kindermann, Sheng-Qi Xiang, Andreas Kronz, Adam Lange, and Franc Meyer, Organometallics, 2014, 33, 1475-1479) in 60 mL of THF, and 18.9 mL of the sodium naphthalide solution from Example 1 was added dropwise with stirring. The resulting mixture was stirred at room temperature for 4 hours. Subsequently, a solution of 548 mg of N,N-dimethylaminopropyl chloride in 10 mL of THF was added dropwise. The reaction mixture was stirred at room temperature for 20 hours, the solvent was removed in vacuo, and the residue was extracted into diethyl ether (stirring time 5 to 20 hours). After removing the diethyl ether in vacuo, the naphthalene still present in the crude product was removed by sublimation in vacuo (55°C). The residue was purified by vacuum distillation and the product was obtained as an oil (approximately 30% yield).

[0052] Example 3b according to the invention (preparation of dicarbonyl(η 5 -cvclopentadienyl)(3-dimethylaminopropvDruthenium Irp-CsHsRufCOMC^^NfCHsk respectively η 5 - CsHsRufCOkDMPI with Na / K alloy):

[0053] 300 mg potassium and 100 mg sodium were weighed into a Schlenk tube and the liquid Na / K alloy was formed by gentle swirling. The alloy was suspended in 20 mL THF and treated at room temperature with a solution of 1.0 g [η 5-C5HsRu(CO)2]2 (prepared according to Kai F. Kalz, Nicole Kindermann, Sheng-Qi Xiang, Andreas Kronz, Adam Lange, and Franc Meyer, Organometallics, 2014, 33, 1475-1479) in 40 mL of THF and stirred at room temperature for 20 h. The solvent was removed in vacuo, and the crude product was treated with 60 mL of diethyl ether. The mixture was then filtered, 548 mg of N,N-dimethylaminopropyl chloride was added at room temperature, and the mixture was stirred again for 20 h at room temperature. The reaction mixture was filtered again, the solvent removed in vacuo, and the remaining dark red, oily crude product was distilled at 65°C in vacuo. The product was isolated as a yellowish oil in a yield of 710 mg (51%).

[0054] Elemental analysis:

[0055] C12H17NO2RU (308.34 g / mol)

[0056] Calculates CHN o Ru

[0057] 46.74% 5.56% 4.54% 10.38% 32.78%

[0058] Found CHNO Ru 47.03% 5.62% 4.53% 10.85% 31.97%

[0059] 1 H NMR (200 MHz, C6D6): δ (ppm) = 4.55 (s, 5H), 2.30 (t, 2H), 2.20 (s, 6H), 1 .84 (quint., 2H), 1.76 (t, 2H).

[0060] 13 C-NMR (50 MHz, C6D6): δ (ppm) = 203.4 (20, n 5 -C5H5Ru(CO)2C3H6N(CH3)2), 88.8 (50, η 5 - C5H5RU(CO)2C3H6N(CH3)2), 64.6 (10, n 5 -C5H5Ru(CO)2CH2CH2CH2N(CH3)2), 46.1 (20, η 5 - C5H5RU(CO)2C3H6N(CH3)2), 38.2 (10, η 5 -C5H5Ru(CO)2CH2CH2CH2N(CH3)2), -5.7 (10, η 5 - C5H5RU(CO)2CH2CH2CH2N(CH3)2).

[0061] LIFDI-MS (m / z): 308.044 = [M] +

[0062] Inventive Example 4 (Preparation of Dicarbonyl(η 5 -cyclopentadienyl)(3-diethylaminopropvDruthenium [η 5 -C5H5Ru(CO)2(CH2)3N(CH2CH3)2 respectively η 5 - C5H5RU(CO)2DEP1 with Na / K alloy):

[0063] The synthesis was carried out analogously to example 3b) with the following substances and weights:

[0064] 300 mg potassium

[0065] 100 mg sodium

[0066] 1 .0 g [n 5 -C5H5Ru(CO)2]2

[0067] 674 mg N,N-diethylaminopropyl chloride

[0068] 810 mg (54%) of the product was isolated as a yellow oil after vacuum distillation at 75 °C.

[0069] Elemental analysis:

[0070] CI4H 21 NO2RU (336.40 g / mol)

[0071] Calculated CHNO Ru

[0072] 49.99% 6.29% 4.16% 9.51% 30.05%

[0073] Found CHNO Ru

[0074] 49.92% 6.27% 4.14% 9.69% 29.98%

[0075] 1 H-NMR (200 MHz, C6D6): δ (ppm) = 4.56 (s, 5H), 2.52 (m, 4H + 2H), 1 .87 (m, 2H), 1 .75 (m, 2H), 1.05 (t, 6H).

[0076] 13 C-NMR (50 MHz, C6D6): δ (ppm) = 203.1 (20, η 5 -C5H5Ru(CO)2C3H6N(CH2CH3)2), 88.6 (50, η5 - C5H5Ru(CO)2C3H6N(CH2CH3)2), 58.1 (10, η 5 -C5H5Ru(CO)2CH2CH2CH2N(CH2CH3)2), 47.6 (20, η 5 -C5H5Ru(CO)2C3H6N(CH2CH3)2), 37.9 (10, η 5 -C5H5Ru(CO)2CH2CH2CH2N(CH2CH3)2), 12.6 (20, η 5 -C5H5Ru(CO)2C3H6N(CH2CH3)2), -5.7 (10, η 5 -C5H5Ru(CO)2CH2CH2CH2N(CH2CH3)2). LIFDI-MS (m / z): 337,010 = [M]

[0077] Comparative Example 5 (Preparation of Dicarbonyl(η 5 -cvclopentadienyl)(ethyl)ruthenium, η 5 - C5H5RU(CO)2(CH2CH3), g 5 -C5H5Ru(CO)2Et with Na / K alloy):

[0078] The synthesis was carried out analogously to example 3b) with the following substances and weights: 300 mg potassium

[0079] 100 mg sodium

[0080] 1 .0 g [η 5 -C5H5Ru(CO)2]2

[0081] 491 mg ethyl bromide

[0082] The product was isolated as a yellow oil after vacuum distillation at 65°C.

[0083] 1H NMR (200 MHz, C6P6): δ (ppm) = 4.53 (s, 5H), 1 .87 (q, 2H), 1 .52 (t, 3H).

[0084] 13 C NMR (50 MHz, C6P6): δ (ppm) = 203.1 (2C, η 5 -C5H5Ru(CO)2(CH2CH3)), 88.6 (5C, η 5 - C5H5Ru(CO)2(CH2CH3)), 30.5 (1C, η 5 -C5H5Ru(CO)2(CH2CH3)), -9.8 (1 C, η 5 - C5H5Ru(CO)2(CH2CH3)).

[0085] Figure 1 shows the ATR-IR spectrum of η 5 -C5H5Ru(CO)2(CH2)3N(CH3)2.

[0086] Figure 2 shows the result of the thermogravimetric analysis of η 5 - C5H5Ru(CO)2(CH2)3N(CH3)2.

[0087] Figure 3 shows the result of the isothermal gravimetric analysis of η 5 - C5H5Ru(CO)2(CH2)3N(CH3)2) at 80 D C, 100°C and 120°C with the evaporation rates E 80º c = 15.1 pg min -1 cm -2 ; Eloo°c = 54.5 pg min -1 cm -2 and E 120ºC = 176.1 pg min -1 cm -2 .

[0088] Figure 4 shows the Liquid Injection Field Desorption Ionization (LIFDI) mass spectrum of η 5 - C5H5RU(CO)2(CH2)3N(CH3)2.

[0089] Figure 5 shows the comparative results of the thermogravimetric analyses of η 5 - C5H5RU(CO)2(CH2)3N(CH3)2, η 5 -C5H5Ru(CO)2(CH2)3N(CH2CH3)2and η 5 -C5H5Ru(CO)2(CH2CH3).

[0090] Figure 6 shows the smoothed derivatives of the thermogravimetric analyses of η 5 -C5H5Ru(CO)2(CH2)3N(CH3)2, η 5 -C5H5Ru(CO)2(CH2)3N(CH2CH3)2and η 5 - C5H5Ru(CO)2(CH2CH3) preserved functions.

Claims

Patent claims 1 . Half-sandwich complexes selected from the group consisting of compounds of the formulas η 5 -C5H5-nR1 nRu(CO)2CmH2mNR2R3 and η 5 -C9H7- p R1 p Ru(CO)2C m H 2m NR2R3, where n = 0, 1, 2, 3, 4 or 5, m = 1, 2, 3, 4 or 5, p = 0, 1, 2, 3, 4, 5, 6 or 7, the radical(s) R1 are independently selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals, and the radicals R2 and R3 are independently selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals.

2. Half-sandwich complexes according to claim 1 selected from the group consisting of compounds of the formula η 5 -C5H5-nR1nRu(CO)2C mH2mNR2R3, where n = 0 or 1, m = 1, 2, 3, 4 or 5, the radical(s) R1 are independently selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals, and the radicals R2 and R3 are independently selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals.

3. Half-sandwich complexes according to claim 2, wherein n = 0, m = 1, 2, 3, 4 or 5, and the radicals R2 and R3 are independently selected from methyl and ethyl.

4. The half-sandwich complex η 5 -C5H5Ru(CO)2(CH2)3N(CH3)2or η 5 - C5H5RU(CO)2(CH2)3N(CH2CH3)2.

5. Half-sandwich complexes according to one of the preceding claims in the form of dimers or oligomers.

6. A process for the preparation of a half-sandwich complex according to claim 1, comprising the reaction of η 5 -C5H5- n R1 nRu(CO)2Hal or η 5 -C9H 7- pR1 PRu(CO)2Hal with an organometallic compound of type MC m H2mNR2R3 or of the type Zn(C m H 2m NR2R3)2or with a Grignard compound of the type Mg(C m H 2m NR2R3)X, where n = 0, 1, 2, 3, 4 or 5, m = 1, 2, 3, 4 or 5, p = 0, 1, 2, 3, 4, 5, 6 or 7, the radical(s) R1 are independently selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals, the radicals R2 and R3 are independently selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals, Hal = CI, Br or I, preferably CI means M = Li, Na or K, and X = CI or Br.

7. A process for the preparation of a half-sandwich complex according to claim 2, comprising the reaction of η 5 -C5H 5.n R1 nRu(CO)2Hal with an organometallic compound of type MC m H2mNR2R3 or of the type Zn(C mH2mNR2R3)2or with a Grignard compound of the type Mg(CmH 2m NR2R3)X, where n = 0 or 1, m = 1, 2, 3, 4 or 5, the radical(s) R1 are independently selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals, the radicals R2 and R3 are independently selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals, Hal = CI, Br or I means M = Li, Na or K, and X = CI or Br.

8. The process according to claim 7, wherein n = 0, m = 1, 2, 3, 4 or 5, and the radicals R2 and R3 are independently selected from methyl and ethyl.

9. The method according to claim 8, wherein C m H2m = (CH2)3and the radicals R2 and R3 each represent methyl or ethyl.

10. A process for the preparation of a half-sandwich complex according to claim 1, comprising reacting the dimer [η 5-C5H5-nR1nRu(CO)2]2 or the dimer [η 5 -C9H7-pR1 P Ru(CO)2]2 with HalC m H2mNR2R3 in the presence of a reducing agent Y, where n = 0, 1, 2, 3, 4 or 5, m = 1, 2, 3, 4 or 5, p = 0, 1, 2, 3, 4, 5, 6 or 7, the radical(s) R1 are independently selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals, the radicals R2 and R3 are independently selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals, Hal = Cl, Br or I, and Y is selected from Li, Na, K, Mg, Ca, Zn, H2, hydrazine, NaK alloy, NaH, lithium naphthalide, sodium naphthalide, potassium naphthalide, NaBH4 and LiAIH4. 11 . A process for the preparation of a half-sandwich complex according to claim 2, comprising reacting the dimer [η 5 -C5H 5-nR1nRu(CO)2]2 with HalCmH2mNR2R3 in the presence of a reducing agent Y, where n = 0 or 1, m = 1, 2, 3, 4 or 5, the radical(s) R1 are independently selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals, the radicals R2 and R3 are independently selected from methyl, ethyl, propyl, isopropyl and the isomeric butyl radicals; Hal = CI, Br or I means, and Y is selected from Li, Na, K, Mg, Ca, Zn, H2, hydrazine, NaK alloy, NaH, lithium naphthalide, sodium naphthalide, potassium naphthalide, NaBH4 and LiAIH4.

12. The process according to claim 11, wherein n = 0, m = 1, 2, 3, 4 or 5, and the radicals R2 and R3 are independently selected from methyl and ethyl.

13. The method according to claim 12, wherein C m H2m = (CH2)a and the radicals R2 and R3 each represent methyl or ethyl.

14. Use of a half-sandwich complex according to any one of claims 1 to 5 or prepared by a process according to any one of claims 6 to 13 as a precursor in a CVD or ALD process for producing a ruthenium layer or a ruthenium oxide layer on a substrate or as a homogeneous catalyst.

15. Use according to claim 14 for producing a ruthenium layer, wherein the substrate is a semiconductor substrate having one or more contact surfaces to be provided with a ruthenium layer.

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