Mono-substituted cyclopentadienes and metal cyclopentadienyl complexes, and synthesis methods thereof

Abstract

To provide mono-substituted cyclopentadienes and metal cyclopentadienyl complexes that may be used as deposition precursors contained in film forming compositions for film depositions in the semiconductor industry, such as the ALD, CVD and SOD.SOLUTION: The mono-substituted cyclopentadienes have the formula in the figure, and the metal cyclopentadienyl complexes are synthesized from the mono-substituted cyclopentadienes. (In the formula: m≥0; C5H5 represents a cyclopentadienyl (Cp) ring where one hydrogen is substituted with R(F)m; and R(F)m is connected to any one of the carbon atoms of the Cp and selected from among i. a C1-C8 linear or branched, saturated or unsaturated fluorohydrocarbyl group containing at least one fluorine atom, ii. a silyl group [SiR'3] with R' being selected from H or a C1-C4 saturated or unsaturated hydrocarbyl group, and the like.)SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to mono-substituted cyclopentadienes and metal cyclopentadienyl complexes used as precursors in film-forming compositions, and methods for their synthesis. The metal cyclopentadienyl complexes are synthesized from mono-substituted cyclopentadienes and include typical (Group I, Group II and Group III metals) and transition metal cyclopentadienyl complexes. [Background technology]

[0002] Cyclopentadienyl complexes of main-group and transition metals have been widely utilized as precursors for the deposition of metal-containing films by various deposition techniques such as chemical vapor deposition (CVD) and atomic layer deposition (ALD), including metal organic CVD (MOCVD), plasma enhanced CVD (PECVD), plasma enhanced ALD (PEALD), etc. To be an optimal precursor for a given process, a transition metal complex needs to meet a combination of requirements such as thermal stability, volatility, low melting point, optimally liquid at room temperature, and the ability to form films of a particular composition over a particular temperature range.

[0003] The chemical and physical properties of metal complexes can be varied over a wide range by the specific choice of substituents on the cyclopentadiene ring. However, a review of the influence of substituents on cyclopentadiene as a ligand in metal complexes (J. Organomet. Chem., 1994, Volume 479, 1-29) noted that no predictions can be made regarding the effects that can be expected from a particular substituent.

[0004] An example for the deposition process is the indium complex In(R-Cp) (R=C 0 ~C 5 aliphatic chain), the complexes InCp and In(Me-Cp) are solids, with R=C 2 ~C 4 The complex is a light-sensitive liquid, where R=C 5The complexes are photostable, volatile liquids. Ang. Chem. (1957), 69, 639-640; J Organomet. Chem. (1972), 42(2), 307-314; J Am. Chem. Soc. (1989), 111(19), 7648-7650; WO 18225668; U.S. Patent Application Serial No. 16,941,088, filed July 28, 2020.

[0005] Yttrium (Y) cyclopentadienyl complexes have also been used as deposition precursors. Complex Y(RCp) 3 (R = Me, Et, Pr) is a solid at room temperature, but Y( n BuCp) 3 , Y( i BuCp) 3 is a liquid species at room temperature. Ytterbium (Yb) compounds with monosubstituted Cp ligands that are heavier and bulkier than PrCp {(R 1 -C 5 H 4 )(R 2 -C 5 H 4 )(R 3 -C 5 H 4 )Yb}(R 1 , R 2 =CF 3 (CH 2 ) 3 ;R 3 =CF 3 (CH 2 ) 2 ) have good volatility at room temperature, whereas ytterbium complexes with EtCp, MeCp ligands are not volatile below 100° C. See WO 0227063; JP 2002338590; U.S. Pat. No. 4,927,670; RU 2547489; U.S. Pat. App. Pub. No. 20090302434.

[0006] Alkylcyclopentadienes are typically synthesized from CpNa and a bromoalkane, or CpMgCl and a bromo- or iodoalkane. U.S. Patent No. 897,542 to Harlan et al. describes the product C 5H 5 It has been disclosed that the yield and subsequent purity of -R is highly dependent on the reaction conditions and the substituents on the alkyl chain, and may result in undesirable levels of impurities and low yields of the desired product. However, commercially available CpMgCl, CpNa are expensive. Their synthesis requires high temperature operation with sodium metal. However, there are safety concerns. See J. Am. Chem. Soc. 1945, 67, 8, 1237-1239; U.S. Patent No. 2,953,607; J. Organomet Chem 684 (2003) 91-104; U.S. Patent No. 8,975,427.

[0007] Monosubstituted cyclopentadiene C 5 H 5 Few reports have presented alternative syntheses of -R. The approach involves catalyzing freshly decomposed cyclopentadiene with liquid NH 3 In NaNH 2 followed by MeEtCHBr to give a mixture of 1- and 2-sec-butylcyclopentadiene in a 6:4 ratio (Seriya Khimicheskaya (1973), (2), 376-383). Alternatively, freshly decomposed cyclopentadiene can be decomposed in liquid ammonia, tetrahydrofuran (THF), or dimethylformamide solvents with KOH, CaO, or CaH 2 (or with bromoalkanes in the presence of ROM (R = Et, iPr, M = Na, K) or CaC2 without the use of a catalyst (Mironov et al., Khimiya i Khimicheskaya Tekhnologiya (1983), 26(6), 759-761). Mironov et al. reported that the best performance of the reaction was achieved without the use of a catalyst and in the presence of liquid ammonia solvent in the presence of CaC2. 2 and CaH 2 (Mironov et al., Seriya Khimicheskaya (1973), (2), 376-383; Mironov et al., SU 520341 T specification).

[0008] On the other hand, WO 9742151 to Gruter et al. discloses that the reaction of CpH, Br-alkanes, KOH and catalyst Aliquat-336 affords di- and tri-substituted C6H2Os rather than mono-substituted cyclopentadienes. 5 H 4 R 2 and C 5 H 3 R 3 (R is alkyl) is disclosed. When the reaction is carried out according to the process in which the solvent is water, it is impossible to isolate the monosubstituted product from the reaction mixture.

[0009] The known and widely used metal cyclopentadienyl precursors are C 5 H 5 -2-C 5 H 11 As shown for the synthesis of supported indium complexes by 5 H 5 It can only be prepared by certain reactions involving —R or alkali metal cyclopentadienyl. 5 H 5 -2-C 5 H 11 The ligand was mentioned by Abel et al. (J. Chem. Soc. (1960), 1321-1324). However, the ligand was not isolated in pure form and in that paper it was described as a molybdenum (Mo) complex RC 5 H 4 Mo(CO) 3 I(R=CHMePr n ) in -C 5 H 4 -2-C 5 H 11 Only the one coordinated with is shown. Compound C 5 H 5 -2-C 4 H 9 are mentioned by Mironov et al. (Seriya Khimicheskaya (1973), (2), 376-383) and Holbova et al. (Chemicke Zvesti (1969), 23(8), 611-615). However, compound C 5 H 5-2-C 4 H 9 was prepared by a different, much more complicated route involving liquid ammonia and chromatographic separation.

[0010] RU2478576 claims that compound C is produced from CpNa and 1-Br-4,4,4-F-butane without characterization. 5 H 5 -1,1,1-3F-C 4 H 6 RU 2478576 discloses the preparation of the highly volatile ytterbium complex Yb(3FBuCp) without characterization. 2 K(Cp-BuF) for the preparation of (3F-PrCp) 3 ) is disclosed in U.S. Pat. No. 8,785,574. 5 H 5 -1,1,1-3F-Bu is disclosed.

[0011] The lithium complex has been disclosed, without characterization or analytical data, by Tirouflet et al. (Tetrahedron Letters (1973), (3), 257-260). LiAlH 4 The complex obtained by reducing Me-Et-Fulvene with is provided, but the synthesis method is not shown.

[0012] International Publication No. 0227063, Japanese Patent Application Publication No. 2002338590 and US JP 2006275545 A teaches the preparation of Y complexes supported by monosubstituted cyclopentadiene ligands from anhydrous yttrium trichloride and the potassium salt of the corresponding ligand. 1 -C 5 H 4 )(R 2 -C 5 H 4 )(R 3 -C 5 H 4 )Yb}(R 1 , R 2 =CF 3(CH 2 ) 3 , R 3 =CF 3 (CH 2 ) 2 ) are supported by the corresponding potassium compounds K(R n -C 5 H 4 ) and YbCl 3 See RU 2547489.

[0013] Burkey et al. (Organometallics 1993, 12, 1331-1337) reported the synthesis of strontium (Sr) and barium (Ba) complexes with substituted cyclopentadiene ligands, M(Cp-R) 2 (M=Sr, Ba) is a potassium compound, e.g., K((C 3 H 7 ) 3 C 5 H 2 ) and SrI 2 Or BaI 2 It is disclosed that it can be prepared only from K((C 3 H 7 ) 3 C 5 H 2 ) and SrCl 2 The reaction does not proceed, and SrCl 2 and K((C 3 H 7 ) 3 C 5 H 2 ) is recovered. Li((C 3 H 7 ) 3 C 5 H 2 ) and SrCl 2 The reaction does not proceed, and SrCl 2 and K((C 3 H 7 ) 3 C 5 H 2Alternatively, U.S. Pat. No. 4,915,988 discloses that Sr and Ba complexes with substituted cyclopentadienyl ligands can only be prepared at high temperatures (500° C. to 600° C.) from pure cyclopentadienyl ligands and Sr or Ba metal.

[0014] Indium complex In(R-Cp) (R=C 0 ~C 4 Aliphatic chains) are prepared by a proprietary reaction starting from InCl and the lithium salt of the ligand (J. Chem. Soc., Dalton Trans., 1981, 2592). 3 and the unique response from NaCp is InCp 3 The synthesis involves a pyrolysis step of InCp, which gives low yields and, in the case of substituted cyclopentadienyl ligands, a mixture of complexes that are difficult to separate. See Organometallics 1989, 8, 346-356; Organometallics 2002, 21, 4632-4640. Summary of the Invention [Problem to be solved by the invention]

[0015] These suggest that in order to prepare a suitable precursor, it is necessary to screen a wide range of substituents R in the metal cyclopentadienyl (or alkali metal cyclopentadienyl) M(Cp-R) complex of a given metal, and to select an ideal combination of starting materials that provide high stability, volatility, and low melting point, ideally making M(Cp-R) liquid at room temperature. Thus, it is necessary to select a substituted cyclopentadiene C that can serve as a starting compound for forming a desired film-forming composition. 5 H 5 There is a need for a simple, robust and economical method for preparing -Rs and / or the corresponding metal complexes. [Means for solving the problem]

[0016] 1. A method for synthesizing a metal cyclopentadienyl complex comprising the steps of: mixing a metal hydroxide, a halide, a cyclopentadiene monomer, an alkaline earth oxide, and a catalyst in a solvent; Selective catalytic carbon-carbon coupling reactions to form monosubstituted cyclopentadienes contacting the monosubstituted cyclopentadiene with a metal compound; and Conversion of monosubstituted cyclopentadienes to metal cyclopentadienyl complexes. The disclosed method may include one or more of the following aspects: further comprising maintaining the temperature in the range of -15°C to 70°C under atmospheric pressure; further comprising maintaining the temperature below 40°C at atmospheric pressure; further comprising maintaining the temperature in the range of 15°C to 35°C at atmospheric pressure; further comprising maintaining the temperature in the range of 20°C to 30°C at atmospheric pressure; further comprising maintaining the temperature below 5°C at atmospheric pressure; · further comprising maintaining the temperature in the range of -5°C to 0°C under atmospheric pressure; · further comprising maintaining a pressure near atmospheric pressure; · further comprising maintaining the air atmosphere; N 2 , further comprising maintaining an inert gas atmosphere, such as a noble gas (i.e., He, Ne, Ar, Kr, Xe); N 2 further including maintaining the atmosphere; further comprising maintaining an Ar atmosphere; further comprising optionally purifying the monosubstituted cyclopentadiene; further comprising purifying the monosubstituted cyclopentadiene; further comprising not purifying the monosubstituted cyclopentadiene; · Approximately 20-400% excess of cyclopentadiene monomer is used relative to the amount of halide; · Approximately 40-80% excess of cyclopentadiene monomer is used relative to the amount of halide; Optimized selectivity of the process is achieved when an approximately 20-400% excess of CpH monomer over R(Hal) or R(F)(Hal) is used; Optimized selectivity of the process is achieved when an approximately 40-80% excess of CpH monomer over R(Hal) or R(F)(Hal) is used; · the metal hydroxide is MOH, where M is a Group I alkali metal; · MOH is NaOH; ·MOH is KOH; the halide R(Hal) or R(F)(Hal), which is a silyl-, amino-, alkyl- or hydrocarbonyl halide or a fluoroalkyl halide, has the formula R(Hal) or R(F)(Hal), Hal being selected from Cl, Br, I; R is oC 1 ~C 8 Linear or branched chain, saturated or unsaturated hydrocarbyl groups; o C containing at least one fluorine 1 ~C 8 linear or branched, saturated or unsaturated fluorohydrocarbyl groups; oR' is H, C 1 ~C 4 A silyl group [SiR' selected from saturated or unsaturated hydrocarbyl groups 3 ]; Each R' is H, F, C containing at least one fluorine atom 1 ~C 4 a silyl group [SiR' selected from saturated or unsaturated fluorohydrocarbyl groups; 3 ];and oEach R 1 and R 2 are independently H or C 1 ~C 6 an amino group [—NR 1 R 2 ] To be selected from; the alkaline earth oxide being MO, where M is a Group II alkaline earth metal; ·MO is CaCO 2 Being; the catalyst is a tertiary phosphonium salt; The catalyst is tetrabutylphosphonium chloride, Bu 4 It is PCl (CAS number: 2304-30-5); The catalyst is 4 Cl(Pent=C 5 H 11 ) or PPh 4 Cl(Ph=C 6 H 5 ) is; the metal compound is an alkylmetal compound selected from MeLi or BuLi; the metal compound is a metal hydride MH, where M is a group I, II or III main group metal or a transition metal selected from K, Na, Sr, Ba, Ga, In, Y or Yb; The metal compound is a metal hydride MH, where M is a typical metal of group I, II or III; the metal compound is a metal hydride MH, where M is a transition metal selected from K, Na, Sr, Ba, Ga, In, Y or Yb; The metal hydride is an alkali metal hydride; · The alkali metal hydride is NaH; · The alkali metal hydride is KH; The solvent is a furan solvent; The solvent is THF; The solvent is Me-THF; Monosubstituted cyclopentadienes include 1-fluorobutyl-cyclopentadiene (C 5 H 5 -1-FC 4 H 10 , C 5 H 5 -1-F-Bu), 2-pentyl-cyclopentadiene (C 5 H 5 -2-C 5H 11 , C 5 H 5 -2-Pent), 2-butyl-cyclopentadiene (C 5 H 5 -2-C 4 H 9 , C 5 H 5 -2-Bu), or 1,1,1-trifluoropropyl-cyclopentadiene (C 5 H 5 -1,1,1-3F-C 4 H 6 , C 5 H 5 -3F-Bu); Monosubstituted cyclopentadienes include 1-fluorobutyl-cyclopentadiene (C 5 H 5 -1-FC 4 H 10 , C 5 H 5 -1-F-Bu); Monosubstituted cyclopentadienes include 2-pentyl-cyclopentadiene (C 5 H 5 -2-C 5 H 11 ) is; Monosubstituted cyclopentadienes include 2-butyl-cyclopentadiene (C 5 H 5 -2-C 4 H 9 , C 5 H 5 -2-Bu); Monosubstituted cyclopentadiene is 1,1,1-trifluoropropylcyclopentadiene (C 5 H 5 -1,1,1-3F-C 4 H 6 , C 5 H 5 -3F-Bu); The metal cyclopentadienyl precursor is Li(C 5 H 4 -2-C 5 H 11 )(Li(Cp-2-Pent), CAS number:2413046-23-6), K(C5 H 4 -2-C 5 H 11 )(K(Cp-2-Pent)), Na(C 5 H 4 -2-C 5 H 11 )(Na(Cp-2-Pent)), K(C 5 H 4 -1-FC 4 H 10 )(K(Cp-1-F-Bu)), K(C 5 H 4 -1,1,1-3F-C 4 H 6 )(K(Cp-1,1,1-3F-Bu)), Li(C 5 H 4 -2-C 4 H 9 )(Li(Cp-2-Bu)) or In(C 5 H 4 -2-C 5 H 11 ) (In(Cp-2-Pent), CAS number: 2364634-67-1); The metal cyclopentadienyl precursor is Li(C 5 H 4 -2-C 5 H 11 ) (Li(Cp-2-Pent), CAS number: 2413046-23-6); Metal cyclopentadienyl precursor is K(C 5 H 4 -2-C 5 H 11 )(K(Cp-2-Pent)); The metal cyclopentadienyl precursor is Na(C 5 H 4 -2-C 5 H 11 )(Na(Cp-2-Pent)); Metal cyclopentadienyl precursor is K(C 5 H 4 -1-FC 4 H 10 )(K(Cp-1-F-Bu)); Metal cyclopentadienyl precursor is K(C 5 H 4 -1,1,1-3F-C 4 H 6 )(K(Cp-1,1,1-3F-Bu)); The metal cyclopentadienyl precursor is Li(C 5 H 4 -2-C 4 H 9 )(Li(Cp-2-Bu)); The metal cyclopentadienyl precursor is In(C 5 H 4 -2-C 5 H 11 )(In(Cp-2-Pent), CAS number: 2364634-67-1).

[0017] The following formula: [ka] (Wherein, m≧0; M is a typical, alkali metal or transition metal; C 5 H 4 The two hydrogens are M and R(F) m R(F) represents a cyclopentadienyl (Cp) ring substituted by m is linked to any one of the carbon atoms of Cp, and I C 1 ~C 8 Linear or branched chain, saturated or unsaturated hydrocarbyl groups; ii) C containing at least one fluorine 1 ~C 8 linear or branched, saturated or unsaturated fluorohydrocarbyl groups; iii) each R' is H, C 1 ~C 4 A silyl group [SiR' selected from saturated or unsaturated hydrocarbyl groups 3 ]; iv) R' is independently H, F, or a C group containing at least one fluorine atom. 1 ~C 4 a silyl group [SiR' selected from saturated or unsaturated fluorohydrocarbyl groups;3 ]; and v) each R 1 and R 2 But H or C 1 ~C 6 an amino group [—NR 1 R 2 ] The disclosed metal cyclopentadienyl complexes may include one or more of the following aspects: ·R is n-Pr, i-Pr, n-Bu, i-Bu, 2-Bu, n-Pent, i-Pent, 2-Pent, n-Hex, i-Hex, 2-Hex, n-Hept, i-Hept, 2-Hept, -CF 3 , -1,1,1-trifluoropropane (-1,1,1-PrF 3 ), -1,1,1-trifluorobutane (-1,1,1-BuF 3 ) or -1-fluorobutane (-1,1,1-BuF); M is a Group I, II or III main group metal or a transition metal; M is selected from K, Na, Sr, Ba, Ga, In, Y or Yb.

[0018] The following formula: [ka] (Wherein, m ≧0; C 5 H 5 is one hydrogen R(F) m R(F) represents a cyclopentadienyl (Cp) ring substituted by m is linked to any one of the carbon atoms of Cp, and aC 1 ~C 8 Linear or branched chain, saturated or unsaturated hydrocarbyl groups; b. C containing at least one fluorine 1 ~C 8 linear or branched, saturated or unsaturated fluorohydrocarbyl groups; c.R' is H, C1 ~C 4 A silyl group [SiR' selected from saturated or unsaturated hydrocarbyl groups 3 ]; d. R' is H, F, or C containing at least one fluorine atom 1 ~C 4 a silyl group [SiR' selected from saturated or unsaturated fluorohydrocarbyl groups; 3 ];and e.Each R 1 and R 2 are independently H or C 1 ~C 6 an amino group [—NR 1 R 2 ] The disclosed mono-substituted cyclopentadienes may include one or more of the following embodiments: ·R is n-Pr, i-Pr, n-Bu, i-Bu, 2-Bu, n-Pent, i-Pent, 2-Pent, n-Hex, i-Hex, 2-Hex, n-Hept, i-Hept, 2-Hept, -CF 3 , -1,1,1-trifluoropropane (-1,1,1- PrF 3 ), -1,1,1-trifluorobutane (-1,1,1-BuF 3 ) or -1-fluorobutane (-1,1,1-BuF).

[0019] Notation and Nomenclature The following detailed description and claims utilize a number of abbreviations, symbols, and terms that are commonly known in the art.

[0020] As used herein, the indefinite articles "a" or "an" mean one or more.

[0021] As used herein, "about" or "approximately" or "approximately" in the text or claims means ±10% of the stated value.

[0022] As used herein, "room temperature" in the text and claims means about 18°C ​​to about 25°C.

[0023] As used herein, "atmospheric pressure" in the text or claims means about 1 atmosphere.

[0024] Standard abbreviations of elements from the periodic table of elements are used herein. It should be understood that elements can be referred to by these abbreviations (e.g., Si means silicon, N means nitrogen, O means oxygen, C means carbon, H means hydrogen, Hal means halogen, F, Cl, Br, I).

[0025] Unique CAS Registry Numbers assigned by the Chemical Abstract Service (ie, "CAS") are provided to identify particular molecules disclosed.

[0026] As used herein, the term "hydrocarbon" means saturated or unsaturated functional groups containing only carbon and hydrogen atoms.

[0027] As used herein, the term "hydrocarbyl" means any monovalent group derived from a hydrocarbon such as methyl or phenyl.

[0028] As used herein, the term "fluorohydrocarbon" means a saturated or unsaturated functional group containing only carbon, hydrogen and fluorine atoms.

[0029] As used herein, the term "fluorohydrocarbyl" means any monovalent group derived from a fluorohydrocarbon.

[0030] As used herein, the term "alkyl group" refers to a saturated functional group containing only carbon and hydrogen atoms. An alkyl group is a type of hydrocarbon. Moreover, the term "alkyl group" refers to a straight chain, branched chain, or cyclic alkyl group. Examples of straight chain alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, and the like. Examples of alkyl groups include, but are not limited to, methyl (Me), butyl (Bu), pentyl (Pent), and the like. Examples of branched chain alkyl groups include, but are not limited to, t-butyl (t-Bu), and the like.

[0031] As used in the disclosed embodiments, the abbreviation "Me" means a methyl group, "Et" means an ethyl group, and "Pr" means a propyl group; "Bu" means a butyl group, and "Pent" ​​means a pentyl group.

[0032] As used herein, the term "fluoroalkyl group" or "fluorinated alkyl group" refers to a saturated functional group that contains carbon, hydrogen, and at least one fluorine. A fluoroalkyl group is a type of fluorohydrocarbon. Furthermore, the term "fluoroalkyl group" refers to a straight-chain, branched-chain, or cyclic fluoroalkyl group.

[0033] As used herein, a "halide" is represented as R(Hal) and / or R(F)(Hal), where Hal is selected from Cl, Br, I, and R is aC 1 ~C 8 Linear or branched chain, saturated or unsaturated hydrocarbyl groups; b. C containing at least one fluorine 1 ~C 8 linear or branched, saturated or unsaturated fluorohydrocarbyl groups; c.R' is H, C 1 ~C 4 A silyl group [SiR' selected from saturated or unsaturated hydrocarbyl groups 3 ]; d. Each R' is H, F, or C containing at least one fluorine atom. 1 ~C 4 a silyl group [SiR' selected from saturated or unsaturated fluorohydrocarbyl groups; 3 ];and e.Each R 1 and R 2 are independently H or C 1 ~C 6 an amino group [—NR 1 R 2 ] is selected from.

[0034] As used herein, the term "CpH" refers to a cyclopentadiene molecule or cyclopentadiene monomer (C 5 H 6 )

[0035] The term "Cp" as used herein means a cyclopentadienyl ring in which one or more hydrogens have been replaced. Cp is 5 H 5 Ring (one hydrogen replaced), C 5 H 4 Ring (two hydrogens replaced), C 5 H 3 ring (with three hydrogens replaced), etc. The term "Cp" as used herein also refers to a cyclopentadienyl anion or a substituted cyclopentadienyl anion, for example, a cyclopentadienyl anion or a substituted cyclopentadienyl anion in a metal cyclopentadienyl complex. As used herein, "cyclopentadienyl" in a metal cyclopentadienyl complex refers to any cyclopentadienyl, including substituted cyclopentadienyl.

[0036] As used herein, "Cp 2 The term "cyclopentadiene dimer (C 10 H1 2 )

[0037] In this specification, one R(F) m The term "monosubstituted cyclopentadiene" is used because only one (m≧0) group is attached to any one of the carbon atoms on the cyclopentadiene ring. Monosubstituted cyclopentadienes have the general formula C 5 H 5 -(R(F) m ) (m≧0, R has the same definition as “halide” above).

[0038] In this specification, homogeneous catalysis is understood to mean a catalyst that is present in the same phase as the reactants.

[0039] Ranges may be expressed herein as from about one particular value and / or to about one other particular value. When such a range is expressed, it is understood that another embodiment is from the one particular value and / or to the other particular value, along with all combinations within that range. Any and all ranges described herein are inclusive of their endpoints (i.e., x=1-4, or x ranging from 1 to 4 includes x=1, x=4, and x=any number in between), regardless of whether the term "inclusive" is used.

[0040] In this specification, the reference to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with that embodiment may be included in at least one embodiment of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments necessarily mutually exclusive of other embodiments. The same applies to the term "implementation."

[0041] As used herein, the term "independently," when used in reference to a description of an R group, should be understood to indicate that the R group in question is selected independently not only from other R groups having the same or different subscripts or superscripts, but also from any additional species of that same R group. For example, the formula MR 1x (NR 2 R 3 ) (4-x) In the formula, x is 2 or 3, and two or three R 1 The groups may be in a mutually exclusive relationship with each other or with R 2 Or R 3 Additionally, unless otherwise specified, it is to be understood that the values ​​of R groups are independent of each other when used in different formulas.

[0042] As used herein, the term "exemplary" is used herein to mean serving as an example, illustration, or illustration. Any aspect or design described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other aspects or designs. Rather, use of the word exemplary is intended to present concepts in a concrete manner.

[0043] Furthermore, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or." That is, unless specified otherwise or clear from the context, "X utilizes A or B" is intended to mean any of the natural inclusive permutations. That is, if X utilizes A, X utilizes B, or X utilizes both A and B, then "X utilizes A or B" is satisfied in any of the foregoing cases. Additionally, the articles "a" and "an," as used in this application and the appended claims, should be construed generally to mean "one or more," unless specified otherwise or clear from the context to be directed to the singular form.

[0044] The foregoing and various other aspects, features, and advantages of the present invention, as well as the invention itself, may be more fully understood by reference to the following detailed description of the invention when considered in conjunction with the following drawings, which are presented for illustrative purposes only and are not intended to limit the invention. [Brief description of the drawings]

[0045] [Figure 1] FIG. 1 is a diagram of a batch process for the selective catalytic synthesis of monosubstituted cyclopentadienes (I) and their corresponding metal Cp complexes (II). [Diagram 2] FIG. 1 is a diagram of a flow process for the selective catalytic synthesis of monosubstituted cyclopentadienes (I) and their corresponding metal Cp complexes (II). [Diagram 3] FIG. 1 is a process flow chart for the synthesis of monosubstituted cyclopentadienes (I) and their corresponding metal Cp complexes (II). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0046] Disclosed are mono-substituted cyclopentadienes, metal cyclopentadienyl complexes, and methods for their synthesis. The disclosed mono-substituted cyclopentadienes are synthesized by selective catalytic carbon-carbon coupling reactions. The disclosed metal cyclopentadienyl complexes are synthesized from the disclosed mono-substituted cyclopentadienes. The disclosed metal cyclopentadienyl complexes include main group (Group I, Group II, and Group III) metal and transition metal cyclopentadienyl complexes, It can also be used as a deposition precursor contained in a film-forming composition for film deposition in the semiconductor industry, such as ALD, CVD, SOD, etc.

[0047] The monosubstituted cyclopentadienes disclosed have the formula: [ka] (Wherein, m ≧0; C 5 H 5 is one hydrogen R(F) m R(F) represents a cyclopentadienyl (Cp) ring substituted by m is linked to any one of the carbon atoms of Cp, and I C 1 ~C 8 Linear or branched chain, saturated or unsaturated hydrocarbyl groups; ii) C containing at least one fluorine atom 1 ~C 8linear or branched, saturated or unsaturated fluorohydrocarbyl groups; iii) R' is H, C 1 ~C 4 A silyl group [SiR' selected from saturated or unsaturated hydrocarbyl groups 3 ]; iv) R' is H, F, C containing at least one fluorine atom 1 ~C 4 a silyl group [SiR' selected from saturated or unsaturated fluorohydrocarbyl groups; 3 ];and v) Each R 1 and R 2 are independently H or C 1 ~C 6 an amino group [—NR 1 R 2 ] ) selected from

[0048] In the above formula (I), the hydrocarbyl group can be an alkyl group; the fluorohydrocarbyl group can be a fluoroalkyl group or a fluorinated alkyl group. Preferably, R is n-Pr, i-Pr, n-Bu, i-Bu, 2-Bu, n-Pent, i-Pent, 2-Pent, n-Hex, i-Hex, 2-Hex, n-Hept, i-Hept, 2-Hept, -CF 3 , -1,1,1-trifluoropropane (-1,1,1-PrF 3 ), -1,1,1-trifluorobutane (-1,1,1-BuF 3 ), or -1-fluorobutane (-1,1,1-BuF). 5 H 5 -R or C 5 H 5 -R(F) m (m≧0) represents a monosubstituted cyclopentadiene (I).

[0049] The disclosed monosubstituted cyclopentadienes (I) can be used to synthesize metal cyclopentadienyl (Cp) complexes (II) for use as deposition precursors in film deposition. The disclosed metal Cp complexes (II) can be main group or alkali metal Cp complexes and / or transition metal Cp complexes. The disclosed metal Cp complexes (II) have the formula: [ka] (Wherein, m≧0; M is a main group metal or a transition metal; C 5 H 4 The two hydrogens are M and R(F) m R(F) represents a cyclopentadienyl (Cp) ring substituted by m is linked to any one of the carbon atoms of Cp, and I C 1 ~C 8 Linear or branched chain, saturated or unsaturated hydrocarbyl groups; ii) C containing at least one fluorine 1 ~C 8 linear or branched, saturated or unsaturated fluorohydrocarbyl groups; iii) each R' is H, C 1 ~C 4 A silyl group [SiR' selected from saturated or unsaturated hydrocarbyl groups 3 ]; iv) R' is independently H, a fluorine atom, or a C group containing at least one fluorine atom. 1 ~C 4 a silyl group [SiR' selected from saturated or unsaturated fluorohydrocarbyl groups; 3 ];and v) Each R 1 and R 2 But H or C 1 ~C 6 an amino group [—NR 1 R 2 ] ) selected from

[0050] In the above formula (II), the hydrocarbyl group can be an alkyl group; the fluorohydrocarbyl group can be a fluoroalkyl group or a fluorinated alkyl group. Preferably, R is n-Pr, i-Pr, n-Bu, i-Bu, 2-Bu, n-Pent, i-Pent, 2-Pent, n-Hex, i-Hex, 2-Hex, n-Hept, i-Hept, 2-Hept, -CF 3 , -1,1,1-trifluoropropane (-1,1,1-PrF 3 ), -1,1,1-trifluorobutane (-1,1,1-BuF 3 ), or -1-fluorobutane (-1,1,1-BuF). M is coordinated to the Cp ring. Preferably, M is a metal of Groups I, II and III, including alkali metals and transition metals including the lanthanides. Preferably, M=Li, Na, K, Ga, In, Sr, Ba, Y or Yb. Hereinafter, M(C 5 H 4 -R), M(Cp-R), M(C 5 H 4 -R(F)) or M(Cp-R(F)) represents the disclosed metal Cp complex (II).

[0051] The disclosed monosubstituted cyclopentadienes (I) and metal Cp complexes (II) are 1 ~C 8 Chain, preferably C 3 ~C 7 The Cp complexes have unbranched and branched alkyl or hydrocarbyl chains R or fluoroalkyl or fluorohydrocarbyl chains R(F) containing chains. This chain length in the ligand may enable the metal Cp complex to tailor the overall complex or precursor properties, i.e., improve stability, lower melting point, tailor the volatility of the molecule to the appropriate precursor in the film forming composition for film deposition.

[0052] C 1 Or C 2 Some substituted cyclopentadienes with ligands and the corresponding alkali metal salts / complexes are known, but the C 5 H 5Information regarding -R is rare or non-existent in the art.

[0053] Exemplary disclosed monosubstituted cyclopentadienes (I) include 1,1,1-trifluorobutyl-cyclopentadiene (1,1,1-BuF 3 -C 5 H 5 , C 5 H 5 -1,1,1,3F-Bu) [ka] 1-Fluorobutyl-cyclopentadiene (1-BuF-C 5 H 5 , C 5 H 5 -1-F-Bu) [ka] 2-Pentyl-cyclopentadiene (2-C 5 H 11 -C 5 H 5 , C 5 H 5 -2-Pent) [ka] 2-Butyl-cyclopentadiene (2-C 4 H 9 -C 5 H 5 , C 5 H 5 -2-Bu) [ka] Trifluoromethyl-cyclopentadiene (CF 3 -C 5 H 5 , C 5 H 5 -3F-Me) [ka] 1,1,1-trifluoropropyl-cyclopentadiene (1,1,1-PrF 3 -C 5 H 5 , C 5 H 5 -1,1,1-3F-Pr) [ka] n-Pentyl-cyclopentadiene (nC 5 H 11 -C 5 H 5 , C 5 H 5 -n-Pent) [ka] etc.

[0054] Exemplary disclosed metal Cp complexes (II) include: K(Cp-n-Pr)(K(C 5 H 4 -nC 3 H 7 )) [ka] Li(Cp-2-Pent)(Li(C 5 H 4 -2-C 5 H 11 ), CAS number: 2413046-23-6) [ka] K(Cp-2-Pent)(K(C 5 H 4 -2-C 5 H 11 )) [ka] Na(Cp-2-Pent)(Na(C 5 H 4 -2-C 5 H 11 )

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[0055] The disclosed synthetic method for synthesizing monosubstituted cyclopentadienes (I) is a selective catalytic carbon-carbon coupling method, which provides a practical and scalable synthetic method by tuning and optimizing reaction conditions to produce products in high yields and minimize the impact of side reactions. The selective catalytic carbon-carbon coupling method uses commonly available starting compounds such as metal hydroxides (e.g., KOH or NaOH), alkyl halides R(Hal) or fluoroalkyl halides R(F)(Hal), cyclopentadiene monomers (i.e., CpH, CAS number: 26912-33-4), alkaline earth oxides (e.g., CaO), tertiary phosphonium salts (e.g., tetrabutylphosphonium chloride, Bu 4 The starting compounds are stable in air. Therefore, it is not necessary to dry the solvent such as THF before synthesis, and the starting compounds and the solvent can be loaded in air. The reaction is carried out under mild conditions at -15°C to 70°C under 1 atm, and is carried out in commonly used glassware or synthesis reactors. This reaction can be applied to the synthesis of a wide range of substituted cyclopentadienes. Here, a tertiary phosphonium salt (e.g., Bu) is used as a catalyst to efficiently and selectively promote the reaction. 4To our knowledge, it is not yet possible in the art to successfully synthesize substituted cyclopentadienes using the combination of the aforementioned starting compounds with the catalytic tertiary phosphonium salts disclosed herein.

[0056] The disclosed mono-substituted cyclopentadienes (I) are prepared from CpH and a silyl-, amino-, alkyl halide R(Hal) or a fluorinated silyl-, amino-, alkyl halide R(F)(Hal), where the halogen is selected from Cl, Br, I. The disclosed method for synthesizing mono-substituted cyclopentadienes (I) includes the use of a metal hydroxide (e.g., KOH or NaOH), an alkaline earth oxide (e.g., CaO), and a catalyst (e.g., Bu 4 The method includes contacting CpH and an alkyl halide R(Hal) or a fluoroalkyl halide R(F)(Hal) in the presence of Cp(Cl) to form a monosubstituted cyclopentadiene (I). The method may further include distilling the monosubstituted cyclopentadiene (I) from the reaction mixture and converting it to a metal Cp complex (II).

[0057] The disclosed method for synthesizing metal Cp complex (II) comprises contacting mono-substituted cyclopentadiene (I) and an alkyl metal compound or an alkali metal hydride in a furan solvent such as THF. The metal Cp complex (II) is formed by a metallation chemical process that occurs in a mixture of mono-substituted cyclopentadiene (I) and an alkali metal hydride such as NaH or KH, or an alkyl metal compound such as an alkyl lithium compound. The method may further comprise removing any volatile species from the metal Cp complex (II).

[0058] Sodium and potassium hydrides are less expensive than the alkyllithium compounds and are safer to operate in large quantities, especially when the compounds are packaged in sealed dissolvable bags or utilized as suspensions in mineral oil. The solvent THF allows for high volumetric efficiency, which is important for scale-up of the reaction.

[0059] For example, from the following examples, the disclosed 2-pentyl-cyclopentadiene (2-C 5 H 11 -C 5 H 5 , H(Cp-2-Pent)) is a solid KOH and CaO and Bu 4 In the presence of PCl catalyst, cyclopentadiene dimer Cp 2 Freshly decomposed CpH and 2-bromopentane (2-Br-C 5 H 11 ) by selective catalytic carbon-carbon coupling reaction. An exemplary reaction scheme is as follows: [ka]

[0060] 2-Bromo-pentane is replaced by n-pentyl-bromide, 2-bromo-butane, iodo-trifluoromethane, 4-bromo-1,1,1-trifluorobutane, 3-bromo-1,1,1-trifluoropropane or 4-bromo-1-fluorobutane to give n-pentyl-cyclopentadiene (nC 5 H 11 -C 5 H 5 ), 2-butyl-cyclopentadiene (2-C 4 H 9 -C 5 H 5 ), trifluoromethyl-cyclopentadiene (CF 3 -C 5 H 5 ), 1,1,1-trifluorobutyl-cyclopentadiene (1,1,1-BuF 3 -C 5 H 5 ), 1,1,1-trifluoropropyl-cyclopentadiene (1,1,1-PrF 3 -C 5 H 5 ), 1-fluorobutyl-cyclopentadiene (1-BuF-C 5 H 5 ) may be produced.

[0061] CpH(C5 H 6 , hereafter referred to as CpH monomer) is a dicyclopentadiene dimer (Cp 2 , C 10 H 12 , CAS Number: 77-73-6) by any suitable means disclosed in the art.

[0062] Freshly decomposed CpH monomer is used for the reaction. Due to its well-known ability to dimerize, the CpH monomer is used immediately after decomposition or stored at low temperatures, between -100°C and -20°C, preferably between -70°C and -40°C. Before use, CpH is always analyzed by proton NMR, GC or any other suitable analytical method to determine the identity of the CpH monomer CpH. 5 H 6 and Cp 2 dimer C 10 H 12 This analysis determines the relative amounts of CpH monomer and Cp for the optimal molar ratio of cyclopentadiene monomer and R(Hal) or R(F)(Hal) in the catalytic C-C coupling reaction. 2 The amount of the mixture containing dimer is calculated.

[0063] The halogens in the starting compound alkyl or hydrocarbyl halide R(Hal) are selected from Cl, Br, I, where R is C 1 ~C 8 A linear or branched, saturated or unsaturated hydrocarbyl group; R' is H, a fluorine atom, C 1 ~C 4 A silyl group [SiR' selected from saturated or unsaturated hydrocarbyl groups 3 ]; or each R 1 and R 2 are independently H or C 1 ~C 6 an amino group [—NR 1 R 2Exemplary R(Hal) include alkyl bromides R-Br or alkyl iodides RI, such as 2-Br-pentane, 2-Br-butane, or 2-Br-propane.

[0064] The halogens in the starting compound fluoroalkyl halide R(F)(Hal) are selected from Cl, Br, I, where R(F) is a C 1 ~C 8 R' is a linear or branched, saturated or unsaturated fluorohydrocarbyl group; or R' is H, F, C containing at least one fluorine atom 1 ~C 4 a silyl group [SiR' selected from saturated or unsaturated fluorohydrocarbyl groups; 3 Exemplary R(F)(Hal) include 1-Br-4,4,4-trifluorobutane, 3-Br-1,1,1-trifluoropropane, 1-Br-4,-fluorobutane, or bromo-trifluoromethane.

[0065] The disclosed selective catalytic carbon-carbon coupling reaction uses an alkali metal hydroxide, M 1 OH (e.g., M 1 = Li, Na, K) and proceed without additives. 2 O (e.g., M 2 =Ca) further promotes mixing of the components and makes the reaction mixture fully stirrable throughout the reaction time, allowing the metallization chemical process to provide high product yields and allowing efficient separation of the solution from the solids after the reaction.

[0066] In one embodiment, monosubstituted cyclopentadiene (I) is selectively synthesized from freshly cracked CpH and an alkyl halide compound R(Hal) or a fluoroalkyl halide compound R(F)(Hal) in THF by using a 1.4-1.6 molar excess of CpH relative to R(Hal) or R(F)(Hal) and maintaining a temperature range of 15-40° C. during the reaction at atmospheric pressure. Since the selective catalytic carbon-carbon coupling reaction is exothermic, cooling the reaction mixture to room temperature is necessary to maintain the high selectivity of the reaction.

[0067] The most important key point in this application is the application of a catalyst that selectively promotes the reaction of CpH with an alkyl halide R(Hal) or a fluoroalkyl halide R(F)(Hal) to obtain the desired monosubstituted cyclopentadiene (I) in high yield. 4 The catalyst may be a tertiary phosphonium salt such as PCl. The suitable amount of catalyst is 0.1-10 mol % based on the amount of R(Hal) or R(F)(Hal). When the catalyst is applied, a conversion rate with high selectivity is achieved in the temperature range of 0 to 70°C, preferably 15 to 30°C.

[0068] To perform the reaction selectively, PPent 4 Cl(Pent=C 5 H 11 ), PPh 4 Cl(Ph=C 6 H 5 Other catalysts such as 1,2-dichlorophenyl ether (1,2-dichlorophenyl ether) may be applied. Based on the comparative examples below, this reaction must be carried out in THF, not in water, and in the presence of calcium oxide in order to have a good yield of the product.

[0069] The reaction is allowed to proceed until all R(Hal) or R(F)(Hal) is consumed. The degree of conversion can be monitored in situ by GC, Raman spectroscopy or other suitable techniques. After conversion, any solids are separated by filtration or decantation. After separation of the solids, the remaining liquid is purified by distillation to remove catalyst, unreacted CpH, Cp 2 and solvents. The products include mono-, di-, and tri-substituted cyclopentadienes (I), which can be separated by distillation, crystallization, or filtration processes.

[0070] The process for the synthesis of monosubstituted cyclopentadienes (I) can be carried out in a batch or flow reactor. Optimized selectivity of the process is achieved when using about 20-400% excess, preferably 40-80% excess, of CpH monomer over R(Hal) or R(F)(Hal).

[0071] The excess CpH monomer should be separated from the reaction product, monosubstituted cyclopentadiene (I), by distillation after the reaction. Due to the low boiling point of the CpH monomer (i.e., 40.8°C), it can be separated into the first fraction during the distillation process. The absence of the CpH monomer can be confirmed by any suitable analytical method, including proton NMR, gas chromatography.

[0072] The reaction product may result from dimerization of the CpH monomer during the catalytic carbon-carbon coupling reaction and distillation of the product after the reaction, or the CpH monomer employed for the reaction may initially be at a certain amount of Cp 2 Due to the inclusion of cyclopentadiene dimer Cp 2 Cp 2 can be separated from the reaction product, mono-substituted cyclopentadiene, by distillation. Alternatively, the mono-substituted cyclopentadiene (I) can be separated from Cp 2The mixture may be used in further steps as a mixture with cyclopentadiene (I). Fractional distillation may proceed below room temperature, or at room temperature, or by moderate heating at temperatures ranging from -30 to 100°C, preferably 0 to 40°C, and at various pressures. Ambient or reduced pressures of 0.01 to 760 Torr or 0.1 to 100 Torr reduce the distillation temperature and the yield of the product mono-substituted cyclopentadiene (I). 5 H 5 This is preferable since it suppresses side reactions such as dimerization of -R.

[0073] Monosubstituted cyclopentadiene C, the product obtained after brief stripping of volatiles from the reaction mixture. 5 H 5 -R(I) and Cp 2 The mixture can be reacted directly with a stoichiometric amount of an alkyllithium reagent such as methyllithium (MeLi) to give all the monosubstituted cyclopentadienes C 5 H 5 -R(I) to the corresponding lithium compound Li(C 5 H 4 -R). After a short stripping of the reaction mixture of volatiles, the product monosubstituted cyclopentadiene C 5 H 5 -R(I) and Cp 2 Cp in a mixture of 2 The relative amount of may vary from 5 to 80% w / w, and the solvent may vary from 1 to 50%. Cp 2 and the solvent was Li(C 5 H 4 -R). 5 H 5 When the reaction of -R with alkyllithium compounds is attempted in non-furan solvents such as diethyl ether, arenes (toluene, xylene, etc.) and alkanes (pentane, hexane, heptane, etc.), stable gels and viscous non-stirring pastes are formed. The addition of furan solvents such as THF, Me-THF (methyltetrahydrofuran) prevents the formation of gels and viscous solutions. The reaction with the alkyllithium compound proceeds smoothly, with good mixing and high volumetric efficiency. Thus, in one embodiment, a furan solvent, preferably THF, is utilized in the reaction, with the relative amount of solvent in the reaction mixture prior to the addition of the alkyllithium reagent being between 20% and 90%. In one embodiment, THF is used to separate the mono-substituted cyclopentadiene (I) and Cp prior to the addition of the alkyllithium compound. 2 to form the metal Cp complex (II).

[0074] The alkyllithium reagent may be MeLi, n-butyllithium, tert-butyllithium or any other suitable alkyllithium compound, neat or in solution in any suitable solvent, preferably ether, toluene, xylene, alkane solvents (pentane, hexane, heptane, and octane).

[0075] The reaction with alkyllithium reagents proceeds in the temperature range of -80°C to room temperature, preferably -10°C to 0°C. Higher temperatures are preferred for cyclopentadienyllithium (LiC 5 H 5 After addition of the alkyllithium compound, the reaction mixture is allowed to warm to room temperature to form Li(C 5 H 4 -R) during which the liberation of gaseous by-products (b-butane, methane, etc.) ceases, followed by stripping of all volatile materials under reduced pressure, which can be from 0.01 Torr to 100 Torr, preferably from 0.1 Torr to 1 Torr.

[0076] Li(C) 5 H 4 The remaining THF solvent is converted to Li(C 5 H 4 The reduced pressure may be from 0.01 Torr to 100 Torr, preferably from 0.1 Torr to 1 Torr.

[0077] In one exemplary embodiment, the monosubstituted cyclopentadiene (I) is 2-pentyl-cyclopentadiene (2-Pent-C 5 H 5 ), then 2-Pent-C 5 H 5 and Cp 2 In a mixture of Cp 2 The relative amount of may vary from 5 to 70% w / w, and the solvent may vary from 1 to 30%. The mixture reacts directly with a stoichiometric amount of MeLi to produce all of the 2-Pent-C 5 H 5 can be converted to the corresponding lithium complex Li(Cp-2-Pent). 2 The solvent can be removed from Li(Cp-2-Pent) by stripping under reduced pressure. An exemplary reaction scheme is shown below: [ka]

[0078] The purity of Li(Cp-2-Pent) is monitored by proton NMR, FTIR, Raman, elemental analysis or any other suitable method. The purity of Li(Cp-2-Pent) is in the range of 90% to 99.99%, preferably 97% to 99.9%, more preferably 99% to 99.9%.

[0079] The following examples demonstrate the disclosed synthesis method, i.e., Cp 2 Lithiation of monosubstituted cyclopentadiene(I) in a mixture with Cp under vacuum. 2 By removing the starting compound 2-Pent-C 5 H 5 Even if the lithium salt is not purified, it is possible to prepare high-purity lithium compounds (purity 99% or higher).

[0080] Alternatively, after the synthesis of monosubstituted cyclopentadiene (I), the reaction mixture is stripped of volatiles in a short time and 5-80% w / w C 5 H 5 -R, 1-50% w / w Cp 2This mixture is reacted directly with an alkali metal hydride such as NaH or KH in a stoichiometric amount relative to the monosubstituted cyclopentadiene (I) to obtain a mixture containing all the C 5 H 5 -R is the corresponding alkali metal Cp complex M(C 5 H 4 -R) (M is preferably Na, K). Cp 2 and the solvent was removed by stripping under reduced pressure to remove M(C 5 H 4 -R). In one exemplary embodiment, THF is removed from 5-80% w / w C 5 H 5 -R, 1-50% w / w Cp 2 , and is added to a mixture containing 1-50% solvent.

[0081] The metal hydride MH (M is a Group I, II or III main group metal or a transition metal selected from K, Na, Sr, Ba, Ga, In, Y or Yb) reagent can be neat or a suspension in mineral oil. The reaction with MH proceeds at a temperature between 0°C and 50°C, preferably between 20°C and 30°C, since higher temperatures promote the undesired dimerization of the monosubstituted cyclopentadiene (I). Once the liberation of hydrogen has ceased, all volatile materials are stripped under reduced pressure. The reduced pressure can be between 0.01 Torr and 100 Torr, preferably between 0.1 Torr and 1 Torr.

[0082] In one exemplary embodiment, 2-Pent-C 5 H 5 After the synthesis of 2-Pent-C 5 H 5 and Cp 2 In the mixture of Cp 2 The relative amount of dimer can vary from 5 to 70% w / w, and the THF solvent can vary from 1 to 30%. The mixture can be reacted directly with a stoichiometric amount of sodium hydride, NaH, to remove all of the 2-Pent-C 5 H 5 may be converted to the corresponding sodium compound Na(Cp-2-Pent). 2and THF are removed from Na(Cp-2-Pent) by stripping under reduced pressure. The reduced pressure or vacuum ranges from 1 Torr to 100 Torr for large scale. An exemplary reaction scheme is shown below. [ka]

[0083] Residual THF solvent can be removed from Na(Cp-2-Pent) by heating under reduced pressure to 220°C, preferably to 200°C. The purity of Na(Cp-2-Pent) is tested by proton NMR, FTIR, Raman, elemental analysis, or any other suitable method. The purity of Na(Cp-2-Pent) is 90%-99.99%, preferably 97%-99.9%, more preferably 99%-99.9%.

[0084] Or 2-Pent-C 5 H 5 After the synthesis of 2-Pent-C 5 H 5 and Cp 2 In this mixture, the relative amount of dimer can vary from 5 to 70% w / w, and the THF solvent can vary from 1 to 30%. The mixture is reacted directly with a stoichiometric amount of potassium hydride (KH) to obtain all of the 2-Pent-C 5 H 5 may be converted to the corresponding potassium compound K(Cp-2-Pent). 2 and the solvent is removed from K(Cp-2-Pent) by stripping under reduced pressure. An exemplary reaction scheme is shown below: [ka]

[0085] Residual THF solvent can be removed from K(Cp-2-Pent) by heating to 150°C under reduced pressure, preferably to 120°C under stirring. The purity of K(Cp-2-Pent) is tested by proton NMR, FTIR, Raman, elemental analysis, or any other suitable method. The purity of K(Cp-2-Pent) is 90%-99.99%, preferably 97%-99.9%, more preferably 99%-99.9%.

[0086] The synthesis and isolation of the monosubstituted cyclopentadiene (I) disclosed herein can be carried out in a batch reactor and comprises the following steps: a) adding an alkali metal hydroxide (e.g., KOH, NaOH), an alkaline earth metal oxide (e.g., CaO) and a suitable solvent into a reactor; b) adding cyclopentadiene monomer into the reactor; c) charging the catalyst into the reactor with or without a solvent; d) stirring the mixture in the reactor with or without cooling to obtain a suspension; e) adding R(Hal) or R(F)(Hal) to the suspension with cooling to maintain a temperature in the range of 0-70°C at 1 atmosphere to form a solution; f) Separating the solids from the solution (optionally with filtration) and adding the solution to a separate distillation apparatus; i. isolating unreacted starting materials; ii. isolating the solvent; iii. isolating the reaction product, monosubstituted cyclopentadiene (I); and iv. Recovering the Solvent (Optional) To enable; g) introducing the recovered solvent into step a); h) drying the monosubstituted cyclopentadiene (I) using molecular sieves; i) introducing the mono-substituted cyclopentadiene (I) into the next step for the synthesis of the metal Cp complex (II) or recovering the mono-substituted cyclopentadiene (I) in a suitable container.

[0087] The synthesis and isolation of the disclosed metal Cp complexes (II) can be carried out in a batch reactor following the production of the monosubstituted cyclopentadiene (I) and comprises the following steps: j) adding a monosubstituted cyclopentadiene (I) into a reactor; k) THF is added to the reactor and the reactor is cooled to -20°C, preferably -5°C, at 1 atm. To do; l) adding an alkyllithium solution, preferably a methyllithium or butyllithium solution, or a suspension of MH in mineral oil, where M is a Group I, II or III metal or a transition metal selected from K, Na, Sr, Ba, Ga, In, Y or Ye, into the reactor, while maintaining the temperature below 5°C, preferably between -5 and 0°C, during the addition of the alkyllithium, or below 40°C, preferably between 20 and 30°C, during the addition of MH; m) warming the reaction mixture to room temperature (optional) to form the metal Cp complex (II); n) removing all volatile materials under reduced pressure; o) heating the resulting metal Cp complex (II) above its melting point under vacuum to remove residual volatile organic products (optional); p) introducing the obtained metal Cp complex (II) into a next step (e.g. for the preparation of a film-forming precursor) or recovering the obtained metal Cp complex (II) in a suitable container.

[0088] FIG. 1 is a diagram of a batch process for the catalytic synthesis of monosubstituted cyclopentadienes (I) and their conversion to metal Cp complexes (II). The batch process for the synthesis of monosubstituted cyclopentadienes (I) is 2It is preferable to carry out the reaction under an inert atmosphere, such as a rare gas (i.e., He, Ne, Ar, Kr, Xe), but some air and water can be tolerated. The starting compounds and solvents do not necessarily need to be purified from water and degassed from oxygen, and the addition of the starting compounds and solvents may be carried out on air. More specifically, the pot reactor 1 is charged with an alkali metal hydroxide (e.g., KOH, NaOH) and an alkaline earth metal oxide (e.g., CaO). A solvent 2, preferably tetrahydrofuran (THF), is fed into the pot reactor 1 via line 13. Solutions of CpH3 and catalyst 4 are sent into the pot reactor 1 via lines 14 and 15, respectively. Lines 13, 14 and 15 are merged into a mixing line 16 that connects to the pot reactor 1. Optionally, the catalyst 4 is added to the pot reactor 1 as a neat compound. The halogen-substituted hydrocarbon R(Hal) or halogen-substituted hydrofluorocarbon R(F)(Hal) (e.g., 2-Br-pentane) reactant 5 is added to the pot reactor 1 via another line 17. The starting compounds, e.g., solvent, CpH, catalyst and R(Hal) or R(F)(Hal) can be added to the pot reactor 1 by pumps (not shown) or by pressure differential. The pot reactor 1 can be a common vessel with stirring means, temperature and pressure control means, and reaction monitoring means. The pot reactor 1 has a cooling function and is maintained at a temperature ranging from about -15°C to about 70°C, preferably from about 15°C to room temperature, or 35°C, and a corresponding pressure of about 1 atm. Reaction monitoring is provided by chromatography (e.g., GC), spectroscopy (e.g., Raman) or any other suitable analytical technique. The reaction can be carried out under nitrogen at 1 atmosphere. After the desired extent of conversion of the starting compounds has been achieved, preferably when the relative amount of R(Hal) or R(F)(Hal) (e.g., 2-Br-pentane) in the reaction mixture is less than 0.1%, more preferably less than 0.01%, by analysis of reaction monitoring, the reaction mixture in pot reactor 1 is filtered through filter 19 (optionally decanted from solids via 19).The filtrate is introduced into a distillation setup 6 to further isolate the reaction product-monosubstituted cyclopentadiene 8 by stripping volatile products via line 21 and discarding waste 7 including pot residue and post-distillation non-volatile materials via line 20. The distilled solvent may be recycled to solvent 2 via line 26. The reaction product, monosubstituted cyclopentadiene 8, i.e., monosubstituted cyclopentadiene (I), may be purified to any desired level, for example, 99.99% (ultra-high purity (UHP)). The less pure product, or Cp. 2 The unpurified crude reaction mixture containing may be utilized to convert the monosubstituted cyclopentadienes (I) to the corresponding metal Cp complexes (II) by metallation chemical processes.

[0089] Prior to the metallization process, the monosubstituted cyclopentadiene 8 is dried by molecular sieves and degassed via line 22. The dried and degassed product 8 is introduced into the pot reactor 9. The solvent 2 sent to the pot reactor 9 is also dried by molecular sieves via line 18. All contacting parts in the pot reactor 9 must be free of air and moisture. The pot reactor 9 is filled with N 2, a noble gas (i.e., He, Ne, Ar, Kr, Xe), a combination thereof, or any other dry / inert environment. The pot reactor 9 can be a typical vessel having stirring means, temperature and pressure control, and reaction monitoring means. The pot reactor 9 has a cooling function and is maintained at a temperature in the range of about -15°C to about 70°C, preferably about -5°C to room temperature, or 30°C, and a corresponding pressure of about 1 atm. For example, for MeLi, the temperature range is -5°C to 0°C, and for MH (e.g., M=Li, Na, K, Ga, In, Sr, Ba, Y, or Yb), the temperature is 20°C to 30°C. The pot reactor 9 is connected to a nitrogen line and has a function of discharging hydrogen, methane, and butane produced in the metallization reaction. The pot reactor 9 has an outlet 23, e.g., a solid addition funnel, for adding an alkyl lithium solution or a solid alkali metal hydride. After completion of metallization, the solid product metal complex 12 is obtained via line 24, the reaction mixture in pot reactor 9 is warmed to room temperature, and all volatile materials are stripped under reduced pressure via line 25 to receiver 11, and waste is discarded. The reduced pressure ranges from 0.05 to 760 Torr, preferably 0.1 to 50 Torr, which helps to reduce the distillation temperature and speed up the distillation process. Optionally, Cp 2 In order to completely capture residual volatile organic species such as tetrahydrofuran and THF, the resulting metal Cp complex(II) 12 may be melted under vacuum with stirring at the final stage of solvent stripping. For example, the sodium complex Na(Cp) may be melted by heating to 200° C. under a reduced pressure of 0.05 to 1 Torr. 5 H 4 -R) (e.g., Na(Cp-2-Pent) from the examples below) and complete removal of THF. The metal Cp complex (II) 12 can be purified to any desired level, e.g., 99.99% (ultra-high purity (UHP)), by storage under vacuum, recrystallization, or other suitable means. Products of lower purity, e.g., 90%-99%, can be purified by other metal complexes, e.g., the hafnium complex HfCl 2 (Cp-2-Pent) 2 Or it can be utilized in a further metathesis reaction to give the indium complex In(Cp-2-Pent).

[0090] Additionally or alternatively, the synthesis and isolation of the disclosed monosubstituted cyclopentadienes (I) can be carried out in a flow reactor and includes the following steps: a. charging a flow reactor with an alkali metal hydroxide (preferably KOH or NaOH) and an alkaline earth metal oxide (preferably CaO); b. preparing a solution of the catalyst in a suitable solvent; mixing a solution of cR(Hal), cyclopentadiene monomer and catalyst in a flow reactor; d. Recirculating the reaction mixture comprising R(Hal), cyclopentadiene monomer and catalyst in a suitable solvent through a flow reactor and monitoring the consumption of R(Hal) by any suitable method (Raman, FTIR spectroscopy, gas chromatography, liquid chromatography, proton NMR spectroscopy); e. Once the required degree of conversion has been confirmed by analytical methods, delivering the reaction mixture to a crude distillation setup; f. i) isolating unreacted starting materials; ii) isolating the solvent; iii) isolating the reaction product, monosubstituted cyclopentadiene (I); and iv) Recovering the Solvent (Optional) isolating the product by distillation allowing g. drying the monosubstituted cyclopentadiene (I) obtained using molecular sieves; and h. Introducing the mono-substituted cyclopentadiene (I) into the next step for the synthesis of the metal Cp complex (II) or recovering the mono-substituted cyclopentadiene (I) in a suitable container.

[0091] The further steps of synthesis and isolation of the disclosed metal Cp complexes (II) from monosubstituted cyclopentadienes (I) in a flow process are similar to those of the batch processes j) to q).

[0092] FIG. 2 is a diagram of a flow process for the catalytic preparation of monosubstituted cyclopentadienes (I) and the corresponding metal Cp complexes (II). The synthesis flow process for monosubstituted cyclopentadienes (I) is 2, preferably under an inert atmosphere such as a noble gas (i.e. He, Ne, Ar, Kr, Xe), although some air and water can be tolerated, and the starting compounds and solvents do not necessarily need to be purified from water and degassed from oxygen, and the addition of the starting compounds and solvents may be carried out on air. More specifically, the flow reactor 1 is charged with an alkali metal hydroxide (preferably KOH or NaOH) and an alkaline earth metal oxide (preferably CaO). A solvent 2, preferably THF, is sent to the flow reactor 1 via line 13. A solution of CpH3 and a catalyst 4 is sent to the flow reactor 1 via lines 14 and 15, respectively. The R(Hal) or R(F)(Hal) (e.g. 2-Br-pentane) reactant 5 is added to the flow reactor 1 via line 17. Lines 13, 14, 15 and 17 are joined in a mixing line 16 that connects to the pot reactor 1. The starting compounds can be added to the flow reactor 1 by a pump (not shown) or by pressure difference. The flow reactor 1 may be a tubular reactor with or without an inert medium such as a glass bed, or may be equipped with pellets of neat alkali metal hydroxides and alkaline earth metal oxides. The flow reactor 1 may be maintained at a temperature ranging from about -25°C to about 70°C, preferably from about 15°C to room temperature, or 30°C, and a corresponding pressure of about 1 atm. The choice of temperature may depend on the starting compounds used in the synthesis of monosubstituted cyclopentadiene (I), as well as the target reaction product, i.e., metal Cp complex (II). The flow reactor 1 may be maintained at a pressure of about 0.1 atm to about 2 atm, preferably about 1 atm. The flow of the starting compounds and reaction mixture in the mixing line 16 is selected to provide a residence time in the flow reactor 1 of about 5 minutes to about 100 minutes, preferably about 5 minutes to about 20 minutes. A small portion of the flow of the reaction mixture after the flow reactor 1 is led to a Raman probe or GC chromatograph 13 through line 28 and is returned into the flow reactor 1 through line 29. The reaction mixture is recycled through the flow reactor 1 until R(Hal) or R(F)(Hal) (eg 2-Br-pentane) is completely consumed according to analytical methods.When the relative amount of R(Hal) or R(F)(Hal) (e.g. 2-Br-pentane) in the reaction mixture is less than 0.1%, preferably less than 0.01%, by analysis, the reaction mixture is collected in optional receiver 1a via line 27 or directly into distillation setup 6 via line 19. Receiver 1a can be any type of trap including, but not limited to, dry ice / isopropanol, dry ice / acetone, refrigerated ethanol, and / or liquid nitrogen traps.

[0093] The reaction mixture in the receiver 1a may be collected in one or more vessels and transported to a new location before carrying out the next process step. Alternatively, the reaction product in the receiver 1a may be filtered through a filter 19 from unreacted solid alkali metal hydroxides, alkaline earth metal oxides, and solid reaction by-products such as potassium bromide (e.g., utilized KOH and 2-Br-pentane), and then introduced into a distillation setup 6, where the reaction product is further isolated from any reactants, reaction by-products, and solvent. Waste 7, including non-volatile residues after distillation, is discarded through line 20, and the separated solvent can be recycled through line 26. Further steps are similar to those in the batch process described above.

[0094] The synthesis of pure monosubstituted cyclopentadienes (I) can be carried out by hydrolysis of the corresponding metal Cp complexes (II) in hydrocarbon solvents (e.g. pentane, hexane, toluene, ether, THF, etc.). The disclosed methods, such as the hydrolysis of potassium Cp compounds K(Cp-2-Pent), apply relatively simple and rapid procedures to obtain pure (i.e., >99%) monosubstituted cyclopentadienes (e.g., C 5 H 5 -2-Pent) is produced in high yields. The potassium salt is a very stable compound and can be transported to any location before use in the synthesis or stored for long periods under nitrogen atmosphere. Therefore, particularly pure monosubstituted cyclopentadiene (I) is obtained from Cp 2If it has a boiling point close to that of the dimer or similar to that of the solvent used and can be separated in pure form by distillation, it is a very convenient starting compound for the simple preparation of the pure ligand.

[0095] The disclosed mono-substituted cyclopentadienes (I) and corresponding metal Cp complexes (II) are intended to be applied in the synthesis of metal-containing precursors in film-forming compositions for film deposition. The alkyl chain of the mono-substituted Cp ligand affects the overall properties of the metal-containing precursor of the film-forming composition. Specifically, the alkyl chain of the mono-substituted Cp ligand lowers the intermolecular contact energy of the M(Cp-R) molecule, leading to a lower melting point and higher volatility of the M(Cp-R) precursor (where M is any main group or transition metal). On the other hand, the alkyl chain of the mono-substituted Cp ligand lowers the intermolecular contact energy of the M(Cp-R) molecule, leading to a lower melting point and higher volatility of the M(Cp-R) precursor (where M is any main group or transition metal). 5 H 5 The fluorine atoms in the alkyl chains of -R(F) can coordinate to the metal center of the M(Cp-R(F)) complex and saturate the metal center, so that no intermolecular contacts are formed, leading to a decrease in the melting point and an increase in the volatility and stability of the M(Cp-R(F)) precursor.

[0096] In particular, monosubstituted cyclopentadienes (I) bearing unbranched and branched alkyl chains R or R(F) containing 3 to 7 carbon atoms and the corresponding metal Cp complexes (II) are of interest, since this chain length in the ligand allows tuning of the overall precursor properties, i.e. improving the stability, lowering the melting point and tuning the volatility of the compounds.

[0097] The disclosed method for synthesizing mono-substituted cyclopentadiene (I) and the corresponding metal Cp complex (II) can be summarized as a flow chart shown in FIG. 3. In step 102, starting materials or compounds are mixed in a solvent (e.g., THF) to form a first mixture. The starting materials may include Cp, R(Hal) or R(F)(Hal), MOH (e.g., KOH or NaOH), alkaline earth oxide (e.g., CaO), and a catalyst (e.g., BuPCl), etc. In step 104, mono-substituted cyclopentadiene (I) is formed from the first mixture at a temperature ranging from about -15°C to about 70°C under 1 atm. Meanwhile, with the formation of mono-substituted cyclopentadiene (I), Cp is generated. 2 In this step, the monosubstituted cyclopentadiene (I) may or may not be purified to remove unwanted volatile by-products, but Cp 2 Since it has a similar volatility to the monosubstituted cyclopentadiene (I), it can remain in the mixture with compound (I) and is removed after forming the corresponding metal Cp complex (II). 2 The mixture containing the dimer and residual solvent from the previous step is mixed with a metal compound, such as an alkyl lithium compound (e.g., MeLi) or an alkali metal hydride (e.g., NAH, KH) in a furan solvent, such as THF, to form a second mixture in step 106. 2 In the presence of Cp in furan solvent, the corresponding metal Cp complex (II) is formed by a metallation reaction in step 108. In this step, the second mixture can be processed by separation of the solid, Cp, a portion of the solvent, the polysubstituted cyclopentadiene, etc. In step 110, Cp 2 The volatile by-products, including Cp, are removed under reduced pressure or vacuum to obtain the pure product of the metal Cp complex (II) at temperatures ranging from about -15°C to about 200°C. Thus, following the above steps, the synthesized monosubstituted cyclopentadiene (I) is not purified and Cp 2 Even if it is a mixture with a solvent, a pure metal Cp complex (II) is obtained.

[0098] The advantages of the disclosed synthesis method are as follows: a) All starting compounds are stable in air and can be operated at ambient conditions, so there is no need to worry about degassing, drying of solvents, ammonia, CaH 2 , CaC 2 , CpNa or Cp(MgC The costs associated with working with air-sensitive and toxic compounds such as CpNa or Cp(MgCl) are eliminated. The laborious and hazardous preparation of CpNa or Cp(MgCl) is eliminated. b) All starting compounds, except for the CpH monomer, are widely available commercially and inexpensively. The CpH monomer is a widely available Cp 2 It can be easily obtained from the dimer. c) The synthesis of monosubstituted cyclopentadienes (I) proceeds under near ambient conditions and tolerates the ingress of air. d) The reaction mixture after the synthesis of monosubstituted cyclopentadiene (I) does not require deep purification before the subsequent metallation step. Special and expensive purification methods such as chromatography are not required. e) Mixtures containing monosubstituted cyclopentadienes (I) can be metallated with commonly available alkali metal hydrides or alkyllithium compounds under near ambient conditions to give the metal Cp complexes (II). Hazardous operations with molten alkali metals are excluded. f) Purification of the reaction mixture containing the metal Cp complex (II) is simple and involves only stripping of volatile substances. No special and expensive purification methods such as chromatography and fractional crystallization are required.

[0099] To the best of our knowledge, the monosubstituted cyclopentadiene C 5 H 5 -R or C 5 H 5 -R(F)(I) and / or the corresponding metal Cp complexes M(Cp-R) or M(Cp-R(F))(II) have never been previously synthesized using the disclosed synthetic methods of selective catalytic carbon-carbon coupling and have never been disclosed as key components for making a film-forming precursor or film-forming composition. EXAMPLES

[0100] The following non-limiting examples are provided to further illustrate embodiments of the present invention, however, the examples are not intended to be exhaustive and are not intended to limit the scope of the invention described herein.

[0101] Experimental procedure Starting materials, solvents, reaction mixtures, and products were analyzed by any appropriate means, such as gas chromatography (GC) equipped with a thermal conductivity detector (TCD), NMR, Raman spectroscopy on portions or aliquots of the flow, etc. All measurements were performed on samples in sealed flasks or quartz cells without contact with the atmosphere.

[0102] Cp 2 (C 10 H 12 The decomposition of CpH was carried out under 1 atm of nitrogen using a commonly used apparatus consisting of a parent flask with a stir bar, a 20-30 cm Vigreux column, an adapter and a receiver flask. This apparatus was connected to a bubbler under 1 atm of nitrogen. The decomposition was carried out by heating the pot containing the cyclopentadiene dimer to a temperature higher than 140 °C (in the range of 140-190 °C) and collecting the decomposed CpH monomer in a receiver cooled with dry ice. The collected monomer was analyzed by GC immediately after each decomposition. By GC, the relative amount of dimer in the decomposition products varied from 17% to 46% for each decomposition. The decomposition products were always stored in dry ice before the next step. For the synthesis of monosubstituted cyclopentadienes, the amount of decomposed fraction was adjusted to the target amount of CpH. 5 H 6 It was recalculated according to the GC data to have a monomer.

[0103] The following Comparative Examples 1 and 2 illustrate the inapplicability of existing synthesis methods to the synthesis of monosubstituted cyclopentadienes.

[0104] Comparative example 1.C 5 H 5 Synthesis of -2-Pent According to the reaction disclosed in WO 9742151, a 500 mL flask was In the flask, KOH (371.8 g, 3250.0 mmol, 60% w / w) in water was added. 3 N(C 16 H 33 )]Cl (10 g, 31.25 mmol), CpH monomer (C 5 H 6 , 8.85g, 133.9mmol), 2-Br-pentane (C 5 H 11 Br, 25.75 g, 170.5 mmol) were sequentially introduced into the flask under stirring. The reaction mixture became a biphasic system containing a liquid aqueous phase and a viscous organic phase. After stirring the mixture for 3 hours at room temperature, a sample of the organic phase was taken for analysis in THF by GC chromatograph. GC results: THF 72.57%, 2-Br-pentane 14.79%, C 5 H 5 -2-Pent 3.07%, Cp 2 Dimer 5.31%, disubstituted ligand C 5 H 5 -(2-Pent) 2 3.66%, trisubstituted ligand C 5 H 5 -(2-Pent) 3 0.16%. Disubstituted ligand C 5 H 5 -(2-Pent) 2 The structural formula of (mixture of isomers) is: [ka] trisubstituted ligand C 5 H 5 -(2-Pent) 3 (mixture of isomers, one shown) [ka] and Cp 2 Dimer.

[0105] A comparison of the relative amounts of starting compounds in WO 9742151 and the present application is shown in Table 1.

[0106] [Table 1]

[0107] In this application, instead of Aliquiat-336, [Me 3 N(C 16 H 33 Two tertiary ammonium salts, Aliquiat-336 (tricaprylmethylammonium chloride, [Me 3 NR]Cl, R=C 8 H 17 ~C 10 H 21 , CAS: 63393-96-4) and [Me 3 N(C 16 H 33 )]Cl (CAS:112-02-7) is only different from the other in that the alkyl chain has 5 to 7 carbon atoms. It is assumed that the catalytic properties of the two surfactants are close to each other.

[0108] The reaction produces monosubstituted cyclopentadiene C 5 H 5 -2-Pent and polysubstituted cyclopentadienes C 5 H 5 -(2-Pent) n (n=2, 3) are produced, but the monosubstituted cyclopentadienes are difficult to separate from the reaction mixture.

[0109] Comparative example 2.C 5 H 5 Synthesis of -2-Pent According to the reaction described by Mironov et al. (Izvestiya Vysshikh Uchebnykh Zavedenii, Khimiya i Khimicheskaya Tekhnologiya (1983), 26(6), 759-761), KOH in water (2a) or solid (2b) (quantities in Table 2, reactions 2a and 2b were added to a 500 mL flask), THF, CpH monomer, 2-Br-pentane were sequentially introduced into the flask under stirring. The reaction mixture was stirred at room temperature for 3 hours, after which an aliquot of the organic phase was taken for analysis and injected into the GC chromatograph.

[0110] Reaction 2a, GC results: CpH (0.6%), THF (77.2%), 2-Br-pentane (17.4%), Cp 2 Dimer (4.8%). C 5 H 5 No coupling products containing -2-Pent were detected by GC.

[0111] Reaction 2b, GC results: CpH (2.3%), THF (77.5%), 2-Br-pentane (16.5%), Cp 2 Dimer (3.2%). C 5 H 5 No coupling products containing -2-Pent were detected by GC.

[0112] The product, monosubstituted cyclopentadiene C 5 H 5 -2-Pent was not detected by GC when solid KOH or KOH solution in water was used. Therefore, CaC 2 or CaH 2 Either a water-reactive solid such as ammonium nitrate or a liquid ammonia solvent is required.

[0113] [Table 2]

[0114] Example 1.C 5 H 5Synthesis of -2-Pent [ka] The differences from Example 1 and Comparative Example 2 are a) the addition of catalyst (to promote the reaction at ambient conditions), and b) an excess of cyclopentadiene monomer (utilized to achieve high selectivity).

[0115] KOH (24 g, 209.5 mmol) and CaO (5.6 g, 100 mmol) were first introduced into the flask, followed by THF (40 mL), CpH (6.33 g, 53.5 mmol, 55% w / w in the decomposition fraction), 2-Br-pentane (5.36 g, 35.5 mmol) and Bu 4 PCl (1 g, 3.4 mmol) was added to the flask in order under stirring. The reaction mixture was stirred at room temperature for 2 h and then analyzed by GC.

[0116] GC results: CpH (1.0%), THF (71.9%), C 5 H 5 -2-Pent(14.0%), Cp 2 Dimer (12.6%), C 5 H 5 -(2-Pent) 2 Isomers (0.2% and 0.3%).

[0117] C 5 H 5 -2-Pent mass spectrum: m / z=136[M] + (C 10 H 16 )(25%), 121[M-Me] + (5%), 107[M-Et] + (10%), 94 [MC 3 H 6 ] + (60%), 93 [MC 3 H 7 ] + (100%), 91 [MC 3 H 7 -2H] + (60%), 79 [MC 4 H 9 ]+ (40%), 77 [M.C. 4 H 11 ] + (45%), 65 [M.C. 5 H 11 ] + (15%). The positive ion pattern observed in the mass spectrum is similar to that calculated.

[0118] Example 2.C 5 H 5 Scale-up synthesis of -2-Pent The reaction setup included a 5 L flask equipped with an overhead stirrer, thermocouple, and addition funnel. The flask had the possibility to be cooled either by a jacketed flask connected to a condenser or by the flask being immersed in a secondary vessel to which a coolant could be added. The flask was connected to a nitrogen line, purged with nitrogen, and pressurized with 1 atm of N 2 The flask was kept below room temperature. KOH (700 g, 10.6 mol) was added to the flask, followed by CaO (300 g, 5.3 mol), THF (1400 g), and TBPC (30 g) (TBPC stands for tetrabutylphosphonium chloride) in that order using a funnel. The contents of the flask were then cooled to about 0-5°C while stirring. Next, Cp containing the CpH monomer was added to the flask. 2 The cooled digestion product (500 g, 6.15 mol CpH, 80% monomer (GC) in digestion, digestion product was kept on dry ice at all times after digestion) was poured into the flask under stirring.

[0119] 2-Br-pentane (601 g, 3.98 mol, molar ratio 2-Br-pentane:CpH=1:1.54) was weighed separately and placed in the dropping funnel (operation can be done in air). The reaction mixture was cooled and 2-Br-pentane was added to the reaction mixture in the flask at a rate of 10-20 mL / min while maintaining the temperature of the reaction mixture within 20-30 °C. After all the 2-Br-pentane was added, it was necessary to cool for some time (about 1 h) to maintain the temperature of the reaction mixture within 20-30 °C. Then, as the temperature started to decrease at a given degree of cooling, cooling was stopped and the reaction mixture was allowed to proceed with stirring at room temperature for about 1.5 h. An aliquot of the reaction mixture was then taken and analyzed by GC. If 2-Br-pentane was absent on GC (or was <0.1% on GC), filtration of the reaction mixture could be performed. If 2-Br-pentane was present on GC (>0.1%), the reaction mixture was stirred at room temperature for an additional 1-1.5 h and reanalyzed by GC. If 2-Br-pentane was not present, the reaction mixture was filtered through a medium glass frit (or alternatively decanted from the solids). The solids remaining in the flask and on the filter were washed with THF in several portions. All the THF filtrates were combined and the flask containing the filtered reaction mixture with a stir bar was connected to a short-path distillation setup. Stirring was started in the flask containing the THF filtrate, dry ice / IPA was placed in the condenser, and the receiving flask was cooled with dry ice (dry ice / IPA). A liquid nitrogen trap may be optionally installed after the receiving flask and before the vacuum line to prevent contamination of the vacuum pump with organic compounds. The short-path distillation proceeded under reduced pressure while stirring the flask containing the filtered reaction mixture (hereafter the parent flask) and while moderately heating the parent flask to facilitate distillation (liquid temperature in the parent flask is always below 0°C). When nearly all the THF has been stripped, the temperature in the parent flask begins to rise rapidly (e.g., from -15°C to about 0-5°C with a vacuum of 1-3 Torr in the line) and the vacuum improves. At this point, the parent flask was removed from the heat, the assembly was backfilled with 1 atm of nitrogen (or helium or argon), and the receiver flask with THF and CpH monomer was removed. The empty parent flask was reconnected to the receiver flask and cooled with dry ice. Stripping of volatiles from the parent flask proceeds under vacuum until the liquid temperature in the parent flask reaches room temperature and the vacuum is in the millitorr region (e.g., 20°C, 80-150 mTorr in the vacuum line). At this point, distillation has essentially stopped and the system is backfilled with 1 atm of nitrogen. An aliquot of the strip fraction was then taken from the receiver flask for GC analysis. The receiver flask was then removed under a stream of nitrogen, and freshly regenerated molecular sieves were added to the liquid in the receiver flask (this may be done in a nitrogen purged glove bag or glove box). After the addition of the molecular sieves, the C 5 H 5 The receiving flask with the solution of -2-Pent was stored in a freezer below -20°C until the next step. In one experiment, 544.6 g of crude product was obtained from the given amount of starting compound. GC results of the product: CpH 1.0%, THF 3.4%, C 5 H 5-2-Pent 78.2%, Cp 2 16.9%, C 5 H 5 -(2-Pent) 2 0.4%. CpH is the Cp at the GC inlet T = 180 °C. 2 It may be derived from pyrolysis of the dimer. C from 2-Br-pentane 5 H 5 The yield of -2-Pent was 77%.

[0120] Example 3.C 5 H 5 -2-C 4 H 9 Synthesis of [ka] As in Example 2, 2-Br-butane was completely consumed in 4 hours (GC). KOH (140 g, 2.1 mol), CaO (60 g, 1.1 mol), THF (300 mL), and TBPC (6 g, 0.02 mol) were sequentially taken into the flask. Cp 2 The decomposition products contained CpH monomer (122 g, 1.48 mol CpH, 80% of the monomer (GC) in the decomposition products) and 2-Br-butane (120.8 g, 0.88 mol, molar ratio 2-Br-butane:CpH=1:1.67). After stripping, C 5 H 5 -2-C 4 H 9 The crude product was obtained in an amount of 182.1 g, containing 46.8% of C from 2-Br-butane. 5 H 5 -2-C 4 H 9 The yield was 79%.

[0121] GC results of crude product: CpH 0.5%, THF 39.9%, C 5 H 5 -2-C 4 H 9 46.8%, Cp 2 12.0%, C 5 H 5 -(2-C 4 H 9 ) 20.6%, {H(2-C 4 H 9 )} 2 0.2%. CpH is the Cp at the GC inlet T = 180 °C. 2 It may be due to thermal decomposition of the dimer. 5 H 5 -2-C 4 H 9 Mass spectrum: m / z=122[M] + (C 9 H 14 )(40%), 107[M-Me] + (12%), 105[M-Me-2H] + (5%), 93[M-Et] + (100%), 91 [MC 2 H 6 -H] + (70%), 79 [MC 3 H 7 ] + (20%), 77 [MC 3 H 9 ] + (50%), 65[ MC 4 H 9 ] + (15%).

[0122] Example 4.C 5 H 5 Synthesis of -1-F-Bu [ka] This new molecule C 5 H 5 -1-F-Bu or C 5 H 5 -1-FC 4 H 10 was prepared as in Example 2. 1-F-4-Br-butane was completely consumed in 3 hours (GC). KOH (6.57 g, 117.1 mmol), CaO (2.86 g, 51.0 mol), THF (35 g), TBPC (0.29 g, 1.0 mmol) were taken and Cp 2The digestion products contained CpH monomer (4.38 g, 53.0 mmol CpH, 80% of the monomer (GC) in the digestion products) and 1-F-4-Br-butane (4.54 g, 29.3 mol, molar ratio 2-Br-butane:CpH=1:1.81). After stripping, 2.55 g of C 5 H 5 9.92 g of crude product containing -1-F-Bu was obtained. 5 H 5 The yield of -1-F-Bu is 62%.

[0123] GC results of crude product: CpH 1.0%, THF 65.4%, C 5 H 5 -1-F-Bu 25.7%, Cp 2 7.4%, C 5 H 5 -(1-FC 4 H 10 ) 2 0.2%. CpH is the Cp at inlet T = 180°C. 2 It may result from thermal decomposition of the dimer.

[0124] C 5 H 5 Mass spectrum of -1-F-Bu: m / z=140[M] + (C 9 H 13 F) (30%), 93 [M-CH 2 CH 2 F] + (20%), 91 [MC 2 H 6 F] + (20%), 80 [MC 3 H 5 F] + (40%), 79 [MC 3 H 6 F] + (100%), 77 [MC 3 H 8 F] + (50%), 66[C 5 H 6 ] + (15%), 65[C 5 H 5 ]+ (5%).

[0125] Example 5.C 5 H 5 -1,1,1-3F-C 4 H 6 Synthesis of [ka] C 5 H 5 -1,1-3F-C 4 H 6 Or C 5 H 5 -1,1-3F-C 4 H 6 was prepared similarly to Example 2. 1-Br-4,4,4-F-butane was completely consumed in 3 hours (GC). KOH (19.87 g, (85%), 0.30 mol), CaO (7.77 g, 0.14 mol), THF (111 g), TBPC (1.70 g, 5.77 mmol) were collected. Cp 2 The digestion products contained CpH monomer (19.25 g, 0.23 mol CpH, (80% of the monomer (GC) in the digestion products)) and 1-Br-4,4,4-F-butane (24.05 g, 0.13 mol, molar ratio 2-Br-butane:CpH=1:1.85). After fractionation by short path, 7.92 g of C 5 H 5 -1,1,1-3F-C 4 H 6 A crude product of 17.59 g was obtained, containing C from 1-Br-4,4,4-F-butane in the fraction. 5 H 5 -1,1,1-3F-C 4 H 6 The yield is 35%.

[0126] GC results of crude product: CpH 1.2%, THF 34.2%, C 5 H 5 -1,1,1-3F-C 4 H 6 44.4%, Cp 2 18.2%, C 5 H 5-(1,1,1-3F-C 4 H 6 ) 2 1.5%, C 5 H 5 -(1,1,1-3F-C 4 H 6 ) 3 0.23%. CpH is the Cp at the GC inlet T = 180 °C. 2 It may result from thermal decomposition of the dimer.

[0127] C 5 H 5 -1,1,1-3F-C 4 H 6 Mass spectrum: m / z=176[M] + (C 9 H 11 F 3 )(30%), 137[M-HF 2 ] + (1%), 109(1%) [C 4 H 4 F 3 ] + , 105(1%)[C 8 H 9 ] + , 93[M-CH 2 CF 3 ] + (12%), 91 [M-CH 2 CF 3 -H 2 ] + (15%), 79 [MC 3 H 4 F 3 ] + (100%), 77[C 6 H 5 ] + (50%), 69 [CF 3 ] + , (5%), 65[C 5 H 5 ] + (50%).

[0128] Example 6. Synthesis of Li(Cp-2-Pent) [ka] This new molecule Li(Cp-2-Pent) or Li(Cp-2-C 5 H 11 ) is the crude product of the C-C coupling reaction (166.6 g of a 70.6% w / w solution, 0.86 mol of C 5 H 5 A 2L Schlenk flask was charged with MeLi (540 mL of a 1.6 M solution, 0.86 mol) in ether under nitrogen and 247.6 g of THF was added to a 2L flask equipped with a thermocouple, stir bar and connected to a nitrogen line under 1 atm of nitrogen. The flask containing the solution was cooled and maintained at a temperature in the range of -10 to 0°C. A separate 1L Schlenk flask was charged with MeLi solution in ether (540 mL of a 1.6 M solution, 0.86 mol) under nitrogen and 247.6 g of C in THF was added while maintaining the temperature in the range of -5 to 5°C. 5 H 5 The MeLi solution was added via cannula to a flask containing a stirred solution of Li(Cp-2-Pent). After all the MeLi was added, the contents of the flask were allowed to warm to room temperature while stirring. When no more gas was released at room temperature, a trap was placed between the flask and the vacuum line. The trap was evacuated and immersed in liquid nitrogen, and all the solvent was removed in the liquid nitrogen trap. At a certain point, when nearly all the solvent had been removed, the contents turned into a fluffy solid and began to melt at about 100 °C into a viscous glassy solid while releasing significant amounts of volatile organic species. All the volatiles were removed from the solid by heating under vacuum. In some experiments, it was necessary to heat under vacuum to 150-180 °C to remove all the volatile organics from the bulk Li(Cp-2-Pent). The contents of the pot were then cooled to near room temperature under dynamic vacuum, the flask was transferred into a glove box, and the contents were analyzed. The yield of Li(Cp-2-Pent) was 120.0 g, and the yield of Cp-2-Pent was 100.0 g. 5 H 5 -98% from 2-Pent. MP 96°C (DSC). A viscous paste was formed, with a phase transition to a liquid at 202°C (DSC). 1 H NMR(THF-d8): 5.48(s,4H,C 5 H 4 ), 2.57(sext,1H,CH 2 CHMe), 1.58(m, 1H, CH(CH 2 )2 Me), 1.39(m, 3H, CH(CH 2 ) 2 Me),1.20(d,3H,CH-Me),0.90(t,3H,CH 2 -Me). 1 The purity by H NMR was 99.5%. The identity and relative amounts of impurities were based on chemical shifts and total intensities of resonances. Representative amounts of impurities for a given procedure: 5 H 5 -2-Pent 0.25%, total of other impurities 0.25%. Li(Cp-2-Pent) is Li(Cp-3-Cp) when the starting 2-Br-pentane contains 3-Br-pentane. 5 H 11 Li(Cp-2-Pent) is a completely new compound (CAS number: 2413046-23-6).

[0129] Example 7. Li(Cp-2-C 4 H 9 Synthesis of [ka] Li(Cp-2-C 4 H 9 ) or Li(C 5 H 5 -2-C 4 H 9 ) was synthesized in the same manner as in Example 6. 177.5 g of the crude product of the CC coupling reaction (46.8% w / w solution, 0.68 mol of Cp-2-C 4 H 9 ), 425.2 mL (0.68 Mol) of a 1.6 M solution of MeLi in Et2O, and 300 g of THF were collected. It was confirmed that gelation occurred when the amount of THF was small. After the reaction, the reaction product was heated to 65 °C under vacuum. The yield was 88 g, and C 5 H 5 -2-C 4 H 9 was quantitatively obtained from 1 H NMR(THF-d8): 5.50 (m, 4H, C 5 H 4 ), 2.54(sext,1H,CH 2CHMe), 1.63(m, 1H, CH(CH 2 ) 2 Me), 1.47(m, 1H, CH(CH 2 ) 2 Me),1.21(d,3H,CH-Me),0.91(t,3H,CH 2 -Me). 1 Purity by H NMR was 98% with a relative amount of coordinated THF of 0.4% and Cp dimer of 0.2%. MP was 193 °C (DSC). Note: CpLi impurity was generated due to overheating of the reaction mixture upon addition of MeLi. Insufficient amount of THF led to gelation, an incomplete reaction, residual MeLi in the sample, and localized overheating resulting in the generation of CpLi impurity.

[0130] Example 8. Synthesis of K (Cp-2-Pent) [ka] This new molecule K(Cp-2-Pent) or K(Cp-2-C 5 H 11 ) was prepared by adding the crude product of the C-C coupling reaction (475 g of a 60.3% solution in THF, C 5 H 5 The flask was then connected to a vacuum / nitrogen line and placed under 1 atm of nitrogen. Separately, solid KH (84.3 g, 2.1 mol) was added to a solid addition funnel under nitrogen (e.g., in a glove box). The solid addition funnel was then filled with N 2 A 200 mL flask was connected under a stream of nitrogen. KH was then added in portions to the stirred THF solution of cyclopentadiene ligand via the solid addition funnel to maintain steady hydrogen evolution while the temperature of the THF solution was maintained below 30° C. by any suitable cooling means. After all the KH was added, the reaction mixture was stirred until hydrogen evolution ceased (approximately 2-3 hours at room temperature). The solid addition funnel was then replaced with N 2The distillation was then removed under vacuum and all volatiles were stripped off under vacuum. After completion of the distillation, the residue in the flask was heated to 100-130 °C and held under vacuum with stirring until evolution of gaseous products ceased (vacuum in the line improved and reached baseline value). At this point, heating was stopped and the parent flask was cooled to near room temperature, transferred into a glove box, and the contents were analyzed. For the given amount of KH, 347.6 g (1.99 mol) of K(Cp-2-Pent) was isolated, which corresponds to a yield of 94.9%. The MP of K(Cp-2-Pent) was 55-56 °C (DSC). 1 H NMR(THF-d8): 5.36 (2H,C 5 H 4 ),5.32(2H,C 5 H 4 ), 2.57(sext,1H,CH 2 CHMe), 1.58(m, 1H, CH(CH 2 ) 2 Me), 1.44(m, 1H, CH(CH 2 ) 2 Me), 1.31(m, 2H, CH(CH 2 ) 2 Me),1.10(d,3H,CH-Me),0.98(t,3H,CH 2 -Me). 1 The purity was 99.9% by 1 H NMR. The identity and relative amounts of the impurities were determined by chemical shifts and resonance The representative amount of impurity for a given procedure is: C 5 H 5 -2-Pent 0.10%. When 2-Br-pentane contains 3-Br-pentane, K(Cp-2-Pent) may contain K(Cp-3-Pent). Since K(Cp-2-Pent) is sensitive to air and moisture, the synthesis process was carried out under an inert atmosphere.

[0131] Example 9. Synthesis of K(H(Cp-1-F-Bu)) [ka] The new molecule K(H(Cp-1-F-Bu) was prepared as described in Example 8. The crude product of the C-C coupling reaction was 7.5 g (40.3% w / w solution, 22.1 mmol.C 5 H 5 The reaction mixture was cooled to keep the temperature below room temperature, and then cooled to 30° C. 5 H 5 To the solution of -1-F-Bu was added KH. After stripping the solvent, the reaction mixture was heated to 40° C. under vacuum. Yield 3.99 g, C 5 H 5 Quantitative from -1-F-Bu. 1 H NMR(THF-d8): 5.37 (m, 4H, C 5 H 4 ), 4.54(t,1H,CH 2 F), 4.45(t, 1H, CH 2 F), 2.51(m, 2H, CH 2 CH 2 F), 1.79(m,2H,CH 2 CH 2 CH 2 ), 1.61(m,2H,Cp-CH 2 ), overlapping with THF resonances from the solvent. The compound contains 3 mol% THF. 1 H NMR of K(THF) 0.03 The purity of (Cp-BuF) was 96.8% w / w, the relative amount of Cp dimer was 0.4% w / w, and CpK was 2.9% w / w. Decomposition occurred at MP = 89-91 °C (DSC).

[0132] Example 10. Synthesis of K (Cp-1,1,1-3F-Bu) [ka] The preparation was similar to that described in Example 9. The crude product of the CC coupling reaction was 17.6 g (45% w / w solution, 45 mmol.C 5 H 5The reaction mixture was cooled to keep the temperature below room temperature, and then cooled to 30° C. 5 H 5 To the solution of -1,1,1-3F-Bu was added KH. After stripping the solvent, the reaction mixture was heated to 50° C. under vacuum. 5 H 5 The yield of K(Cp-1,1,1-3F-Bu) from -1,1,1-3F-Bu was 10.32 g, which was quantitative. 1 H NMR(THF-d8): 5.40 (m, 4H, C 5 H 4 ), 2.57(t,2H,CH 2 CF 3 ), 2.24(m,2H,CH 2 CH 2 CF 3 ), 1.80(m,2H,Cp-CH 2 ), overlapping with the THF resonance. The compound contains 4 mol % THF. 1 H NMR of K(THF) 0.04 (Cp-BuF 3 The purity of ) was 96.4%w / w, the relative amount of Cp dimer was 0.4%w / w, and CpK was 3.3%w / w. MP decomposed at 105℃ and 155℃ (DSC).

[0133] Example 11. Synthesis of Na(Cp-2-Pent) [ka] This new molecule Na(Cp-2-Pent) or Na(Cp-2-C 5 H 11 ) was prepared similarly to K(Cp-2-Pent) (Example 8). The THF from Na(Cp-2-Pent) could be completely removed by heating at 150-200°C with stirring under vacuum. Yield: 95.8% on 160g scale; MP 110°C (DSC); 1 H NMR(THF-d8): 5.51 (d, 4H, C 5 H 4 ), 2.64(sext,1H,CH2 CHMe), 1.58(m, 1H, CH(CH 2 ) 2 Me), 1.40-1.20(m,3H,CH(CH 2 ) 2 Me),1.17(d,3H,CH-Me),0.92(t,3H,CH 2 -Me). 1 The purity by H NMR was 99.6%. The identity and relative amounts of impurities were based on chemical shifts and total intensities of resonances. Representative amounts of impurities for a given procedure: 5 H 5 -2-Pent 0.20%, other impurities Total 0.2%. If the starting 2-Br-pentane contains 3-Br-pentane, Na(Cp-2-Pent) is Na(Cp-3-C 5 H 11 ).

[0134] Example 12. Pure (>99%) C from the hydrolysis of K(Cp-2-Pent) 5 H 5 Synthesis of -2-Pent A 2 L three-neck flask equipped with a stir bar, thermocouple, and dropping funnel was charged with K(Cp-2-Pent) (321.1 g, 1.842 mol) and 1 L of pentane under nitrogen. The flask was connected to a vacuum line under 1 atm of nitrogen. K(Cp-2-Pent) was suspended in pentane by stirring (i.e., K(Cp-2-Pent) and pentane formed two liquid layers). Deionized and degassed water (100.8 g, 5.526 mol) was charged to the dropping funnel under nitrogen. Water was added from the dropping funnel to the stirred solution of K(Cp-2-Pent) in pentane under nitrogen. During the addition of water, the temperature of the reaction mixture was maintained near room temperature by any suitable cooling means (e.g., an external condenser or the addition of ice in a secondary vessel). After all the water was added, the resulting mixture was stirred under nitrogen for 1 h, then further water was added in air, after which the organic layer was separated using a separatory funnel. The aqueous solution was washed with pentane and the pentane fractions were combined. The pentane solution was diluted with MgSO 4 After drying with MgSO 4The filtrate was placed in a 2 L flask and the pentane was stripped under vacuum to give 237.6 g of product. 5 H 5 It was a mixture of 85.6% w / w (GC) of 2-Pent and 14.4% w / w (GC) of pentane. 5 H 5 The yield of -2-Pent was 81%. 5 H 5 The product was kept below -20°C to prevent dimerization of -2-Pent. 5 H 5 -2-Pent dimerizes at room temperature at a rate of 4.5% / day.

[0135] C 5 H 5 -2-Pent and pentane are separated by fractional distillation, and C with a purity of 99% or more is obtained. 5 H 5 -2-Pent was produced. 1 H NMR, (C 6 D 6 ):6.51, 6.45, 6.34, 6.22, 6.16, 5.94 (Cp-ring C of two isomers) sp2 -H), 2.78, 2.69 (Cp-ring C of two isomers sp3 -H), 2.49 (overlapping multiplet of two isomers Cp-CHMe(Pr)), 1.51, 1.37, 1.28, 1.21 (overlapping multiplet, CH(CH 2 ) 2 Me), 1.13, 1.05 (d, 3H, CH-Me of two isomers), 0.98, 0.95 (overlapping multiplets of two isomers CH 2 -Me). The structures of the two isomers are as follows: [ka]

[0136] By hydrolysis of the potassium compound of the disclosed method, a relatively simple and rapid procedure can be applied to obtain pure monosubstituted cyclopentadiene ligands (e.g., C 5 H 5-2-Pent) is produced in high yields. The potassium salt is a very convenient starting compound for the simple preparation of pure ligands, since it is a very stable compound and can be transported to any location or stored for long periods under nitrogen atmosphere before use in the synthesis.

[0137] Example 13. Synthesis of In(Cp-2-Pent) [ka] The examples given are provided to show that In(Cp-2-Pent) can be prepared only from the lithium compounds Li(Cp-2-Pent) and InCl, and only in ether, as shown in Table 3.

[0138] M(Cp-2-Pent) (3-20 mmol) (M=Li, Na, K) was mixed with stoichiometric amount of In(Hal) (Hal=Cl, Br, I), solvent was added and the mixture was stirred at selected temperature for given time. After that, the mixture was filtered and the solvent was removed under vacuum at room temperature, after which the residue was kept under vacuum in the range of room temperature to 70°C and all volatiles were collected in a separate flask cooled by liquid nitrogen. The residue after solvent stripping and vacuum distillation at room temperature to 70°C was weighed and analyzed by FTIR and NMR.

[0139] [Table 3]

[0140] Sodium and potassium compounds did not react with InCl, whereas InI and InBr produced the desired indium complexes in low yields and with inadequate selectivity, with the product containing 2.5-3.0% InCp and up to 9% ligand C. 5 H 5 The lithium compounds Li(Cp-2-Pent) and InCl alone in ether (reaction 8) give In(Cp-2-Pent) in high yield and high selectivity.

[0141] Example 14. Scale-up synthesis of In(Cp-2-Pent) A 2 L flask containing Li(Cp-2-Pent) (129.9 g, 0.91 mol) was charged with InCl (137.3 g, 0.91 mol) and ether (529 g) at room temperature and stirring was started and continued overnight; the next day, the InCl had disappeared visibly and a fine grey suspension was present. This suspension was filtered through a medium size glass frit (GB medium) and the filtrate was collected in a second 2 L flask. The ether solvent was stripped until the temperature of the liquid in the second 2 L flask was about 15 °C to room temperature. The resulting crude reaction product containing 90-95% In(Cp-2-Pent) was subjected to fractional distillation under vacuum. The first fraction was collected in a dry ice / isopropanol cooled receiver at 50-73.1 °C and 3-4 mTorr vacuum and contained C. 5 H 5 The second fraction, collected in a separate receiver cooled with dry ice / isopropanol at 73.1-73.7 °C and 3-4 mTorr vacuum, was >98% pure In(Cp-2-Pent).

[0142] Starting with crude In(Cp-2-Pent) (185.5 g), GC integration showed 1.6% Et 2 O, 2.7% H(Cp-2-Pent), 95.5% In(Cp-2-Pent) and 0.2% In(Cp-2-Pent) n (n=2, 3), and the first fraction contained 24.7g (13.3% C 5 H 5 -2-Pent and 86.6% In(Cp-2-Pent) (GC integral)) were recovered, and 156.4 g (0.9% C 5 H 5 -2-Pent and 99.0% of In(Cp-2-Pent) (GC integral)) were recovered, leaving 2.2 g of a red liquid in the pot, which was found to be In(Cp-2-Pent) by GC. n (n = 1-3). In(Cp-2-Pent) is a completely new compound (CAS number: 2364634-67-1).

[0143] Although the subject matter described herein may be described in the context of example implementations for processing one or more computing application functions / operations of a computing application having a user-interactive component, the subject matter is not limited to these particular embodiments. Rather, the techniques described herein may be applied to any suitable type of user-interactive component execution management method, system, platform, and / or device.

[0144] It will be understood that many additional changes in the details, materials, steps, and arrangements of parts described and illustrated herein to explain the nature of the invention may be made by those skilled in the art within the principles and scope of the invention as expressed in the appended claims.Accordingly, the invention is not intended to be limited to the specific embodiments in the examples given above and / or in the accompanying drawings.

[0145] Although embodiments of the present invention have been shown and described, modifications thereof may be made by those skilled in the art without departing from the spirit or teachings of the invention. The embodiments described herein are illustrative and not limiting. Many variations and modifications of compositions and methods are possible and are within the scope of the present invention. Thus, the scope of protection is not limited to the embodiments described herein, but is limited only by the claims which follow, the scope of which is intended to include all equivalents of the subject matter of the claims.

Claims

1. The following formula: 【Chemistry 1】 (Wherein m is ≧0; M is a main group, alkali metal or transition metal; C ５ H ４ is a compound in which two hydrogen atoms are M and R(F) ｍ R(F) represents a cyclopentadienyl (Cp) ring substituted by ｍ is linked to any one of the carbon atoms of Cp, and i) C containing at least one fluorine １ ~C ８ Linear or branched, saturated or unsaturated fluorohydrocarbyl groups; ii) each R' is H, C １ ~C ４ a silyl group [SiR' selected from saturated or unsaturated hydrocarbyl groups; ３ ]; iii) R' is independently H, F, or a C group containing at least one fluorine atom. １ ~C ４ a silyl group [SiR' selected from saturated or unsaturated fluorohydrocarbyl groups; ３ ];and iv) Each R １ and R ２ is H or C １ ~C ６ an amino group [—NR １ R ２ ] cyclopentadienyl complexes having a structure selected from the group consisting of

2. R is -CF ３ , -1,1,1-trifluoropropane (-1,1,1-PrF ３ ), -1,1,1-trifluorobutane (-1,1,1-BuF ３ 2. The metal cyclopentadienyl complex of claim 1, wherein the metal cyclopentadienyl complex is selected from -1-fluorobutane (-1,1,1-BuF).

3. 2. The metal cyclopentadienyl complex of claim 1, wherein M is selected from K, Na, Sr, Ba, Ga, In, Y or Yb.

4. The following formula: 【Chemistry 2】 (Wherein, m ≧0; C ５ H ５ is one hydrogen atom R(F) ｍ R(F) represents a cyclopentadienyl (Cp) ring substituted by ｍ is linked to any one of the carbon atoms of Cp, and i. C containing at least one fluorine atom １ ~C ８ Linear or branched, saturated or unsaturated fluorohydrocarbyl groups; ii. R' is H, C １ ~C ４ a silyl group [SiR' selected from saturated or unsaturated hydrocarbyl groups; ３ ]; iii. R′ is H, F, or C containing at least one fluorine atom １ ~C ４ a silyl group [SiR' selected from saturated or unsaturated fluorohydrocarbyl groups; ３ ];and iv. Each R １ and R ２ are independently H or C １ ~C ６ an amino group [—NR １ R ２ ] cyclopentadiene having a substituent selected from the group consisting of cyclopentadiene,

5. R is -CF ３ , -1,1,1-trifluoropropane (-1,1,1-PrF ３ ), -1,1,1-trifluorobutane (-1,1,1-BuF ３ 5. The monosubstituted cyclopentadiene of claim 4, selected from -1-fluorobutane (-1,1,1-BuF).

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