Patent ID: 6723676
Filing Date: 2004-04-20
Classification: C07F

Abstract:
A process for the production of organometallic compounds of transition metals with 2-indenyl as ligand disubstituted in the 1,3-position, that correspond to the general formula (I), whereinA denotes the benzo system or the tetrahydrocyclohexyl system, Q1, Q2 are identical or different and, as substituent of the 2-indenyl system substituted in the 1,3-position, denote hydrogen, C1-C4-alkyl, C6-C14-aryl, C7-C10-aralkyl, C1-C4-alkoxy, C1-C4-alkylthio, phenoxy, phenylthio, di-C1-C4-alkylamino, C6-C14-aryl-C1-C4-alkylamino, di-C6-C14-arylamino, dibenzylamino, tri-C1-C4-alkylsilyl, di-C1-C4-alkylboranyl, phenyl-C1-C4-alkylboranyl, diphenylboranyl, di-C1-C4-alkylphosphoryl, diphenylphosphoryl or phenyl-C1-C4-alkylphos-phoryl, Q3 are identical or different and, as substituent of the 2-indenyl system substituted in the 4,5,6,7-position, denote hydrogen, C1-C4-alkyl, C6-C14-aryl, C7-C10-aralkyl, C1-C4-alkoxy, C1-C4-alkylthio, phenoxy, phenylthio, di-C1-C4-alkylamino, C6-C14-aryl-C1-C4-alkylamino, di-C6-C14-arylamino, dibenzylamino, tri-C1-C4-alkylsilyl, di-C1-C4-alkylboranyl, phenyl-C1-C4-alkylboranyl, diphenylboranyl, di-C1-C4-alkylphosphoryl, diphenylphosphoryl or phenyl-C1-C4-alkylphosphoryl, M1 is a transition metal from Group IV, V or VI of the Periodic System of the Elements according to IUPAC 1985, X denotes an anion, n is a number from zero to 4 that is determined by the valency and the bonding state of M1, m is a number from zero to 4 that is determined by the number of the radicals Q3, Y is a bridge selected from the group consisting of â€”C(R1R2)â€”, â€”Si(R1R2)â€”, â€”Ge(R1R2)â€”, â€”C(R1R2)â€”C(R3R4)â€”, â€”C(R1R2)â€”Si(R3R4)â€” or â€”Si(R1R2)â€”Si(R3R4)â€”, wherein R1, R2, R3 and R4 independently of one another denote hydrogen, halogen, straight-chain or branched C1-C10-alkyl, C5-C8-cycloalkyl, C6-C14-aryl or C7-C10-aralkyl, and Z is a second ligand from the group of open-chain and cyclic, optionally anionic &pgr;-systems, â€”N(R5)â€”, â€”P(R6)â€”, |N(R5R7)â€”, |P(R6R8)â€”, â€”Oâ€”, â€”Sâ€”, |OR5â€” or |SR5â€”, wherein the vertical lines to the left of the element symbol N, P, O and S denotes an electron pair, and the bonding between Z and M1 is ionic, covalent or co-ordinative, and wherein R5, R6, R7 and R8 independently of one another have the same range of meanings as R1 to R4, and R5 and R7 may, in addition denote â€”Si(R1R2R3), and R6 and R8 may in addition denote â€”Si(R1R2R3), â€”OR1, â€”SR1â€” or â€”N(R1R2), comprising the step of reacting a halogenated indene substituted in the 1,3-position of the formula in which Hal1 denotes Cl, Br or I and Q1, Q2 and Q3 have the above meanings, with an elementary metal selected from Groups I, II or XII of the Periodic System according to IUPAC 1985 or a corresponding metal compound in an amount in the range from 1 to 100 moles of elementary metal/metal compound per mole of (II) and with a dihalide of the bridge Y of the formula Hal2â€”Yâ€”Hal3â€ƒâ€ƒ(III), in whichHal2 and Hal3 independently of one another denote Cl, Br or I and Y has the above range of meanings, in an amount of 1 to 20 moles of (III) per mole of (II), wherein if Y has the meaning â€”Si(R1R2)â€”, â€”Ge(R1R2)â€” or â€”Si(R1R2)â€”Si(R3R4)â€”, the reaction of (II) with (i) elementary metal/metal compound, and of (ii) with (III) may also take place simultaneously, and the reaction product of the formula wherein Q1, Q2, Q3, Y, Hal3 and m have the above meanings, is reacted, optionally after it has been separated, with a Z derivative of the formula ZM2pâ€ƒâ€ƒ(Va) or ZR9pâ€ƒâ€ƒ(Vb), in whichM2 denotes Li, Na, K or â€”MgHal4, wherein Hal4 has the range of meanings of Hal2, p represents the number 1 or 2, R9 denotes hydrogen, â€”Si(R1R2R3) or â€”Sn(R1R2R3), and Z, R1, R2 and R3 have the above meanings, with the release of a compound of the formula M2Hal3â€ƒâ€ƒ(VIa) or R9Hal3â€ƒâ€ƒ(VIb), in which M2, R9 and Hal3 have the above meanings, optionally in the presence of an auxiliary base to form the 2-indenyl compound of the formula in which Q1, Q2, Q3, Y, Z and m have the above meanings and which may be present as a dianion, and in which Z may, furthermore, carry M2, R9 or an electron pair, and is then reacted further with a transition metal compound of the formula M1Xqâ€ƒâ€ƒ(VIII), in whichM1 and X have the above meanings and q is a number from 2 to 6 that is determined by the oxidation state of M1.