| 主权项 |
1. A process for the production of silahydrocarbons, comprising:
reacting at least one first reactant with at least one second reactant in the presence of a catalyst, to produce silahydrocarbons having the general formulae R1R2R3R4Si, R1R2R3Si(Q)SiR1R2R3, R5R6R7R8Si, R5R6R7Si(Q)SiR5R7R8, (R1)2Si[QSi(R1)3]2, R1Si[QSi(R1)3]3, or Si[QSi(R1)3]4, wherein R1, R2, R3, R4, R5, R6, R7, and R8 are selected from the group consisting of aliphatic, aryl, alkaryl, aralkyl, and cycloaliphatic univalent hydrocarbyl groups having from one to thirty carbon atoms, with the proviso that at least one of R5, R6, R7, or R8 has an alkenyl functional group; and Q is a straight or branched alkylene group having from two to twenty carbon atoms; wherein the first reactant comprises olefins of 2 to 30 carbon atoms and alkenylsilanes of general formulae (R1)2Si(Rk)2, (R1)3Si(Rk), (R1)Si(Rk)3, or Si(Rk)4 wherein Rk is an alkenyl group of two to thirty carbons and R1 is an aliphatic, aryl, alkaryl, aralkyl, and cycloaliphatic univalent hydrocarbyl groups having from one to thirty carbon atoms; wherein the second reactant comprises monosilane (SiH4) and hydridosilanes of general formulae, R′SiH3, (R′)2SiH2, or (R′)3SiH, or (R′)nH3-nSiQSi(R′)yH3-y wherein n is 0, 1, 2, or 3, y is 0, 1, 2, or 3, n+y≧1 R′ is an aliphatic, aryl, alkaryl, aralkyl, and cycloalpihatic univalent hydrocarbyl group having from one to thirty carbon atoms such as methyl, ethyl, octyl, octadecyl, phenyl, tolyl, phenylethyl, mesityl, and cyclohexylpropyl; and wherein the catalyst comprises iron complexes of terdentate pyridine diimine ligands of Formulae (I) or (II), or a cobalt complex of Formula (III): wherein: G is Fe; each occurrence of R1, R2, R3, R4, R5, R6, R7, R8, and R9 is independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent, wherein R2-R9, other than hydrogen, optionally contain at least one heteroatom; each occurrence of R23 is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R23 optionally contains at least one heteroatom; optionally, any two of R1, R2, R3, R4, R5, R6, R7, R8, R9, and R23 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure wherein L1-L2 is wherein each occurrence of R10, R11, R13, R14, R15, and R16 is independently hydrogen, C1-C18 alkyl, C2-C18 alkenyl, or C2-C18 alkynyl, wherein R10, R11, R13, R14, R15, and R16, other than hydrogen, optionally contain at least one heteroatom, and R10, R11, R13, R14, R15, and R16, other than hydrogen, are optionally substituted, each occurrence of R12 is independently C1-C18 alkylene, C1-C18 substituted alkylene, C2-C18 alkenylene, C2-C18 substituted alkenylene, C2-C18 alkynylene, C2-C18 substituted alkynylene, arylene, substituted arylene, wherein R12 optionally contains at least one heteroatom; optionally any two of R10, R11, R12, R13, R14, R15, R16 taken together form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure; each occurrence of R17 and R18 is independently alkyl, substituted alkyl, aryl, or substituted aryl, wherein each of R17 and R18 optionally contains at least one heteroatom, and wherein R17 and R18 taken together optionally form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure; each occurrence of R19 and R20 is independently a covalent bond that connects Si and C, an alkylene, substituted alkylene, or a heteroatom, wherein R19 and R20 optionally contain at least one heteroatom; wherein L1-L2 bonds with G through unsaturated sites S1 and S2; each occurrence of Ar is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein Ar optionally contains at least one heteroatom; Z is independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent; R7, R8 and R9 are independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent; X is N2, CO, alkyl, OH, SH, SeH, —H, or SiR3 where R is an alkyl, aryl, or siloxanyl group; with the provisos that (1) R1 in Formula (I) is hydrogen, methyl, ethyl or n-propyl; and (2) L1-L2 of Formula (A) is selected from the group consisting of 1,3-divinyltetramethyldisiloxane, 1,3-butadiene, 1,5-cyclooctadienes, dicyclopentadienes, and norbornadienes. |
