Synthesis, Structure, and Reactivity of (tBu2PC2H4PtBu2)Ni(CH3)2 and {(tBu2PC2H
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- 作者：Ingrid Bach ; Richard Goddard ; Carsten Kopiske ; Klaus Seevogel ; and Klaus-Richard Pö ; rschke
- 刊名：Organometallics
- 出版年：1999
- 出版时间：January 4, 1999
- 年：1999
- 卷：18
- 期：1
- 页码：10 - 20
- 全文大小：321K
- 年卷期：v.18,no.1(January 4, 1999)
- ISSN：1520-6041
文摘
Oxidative addition of CH3I to (dtbpe)Ni(C2H4) (dtbpe = tBu2PC2H4PtBu2) affords (dtbpe)Ni(I)CH3 (1). The reaction of (dtbpe)NiCl2 or 1 with the stoichiometric quantity of (tmeda)Mg(CH3)2 yields (dtbpe)Ni(CH3)2 (2). (dtbpe)Ni(I)CD3 (1-d3) and (dtbpe)Ni(CD3)2 (2-d6) havebeen prepared analogously. Thermolysis of 2 in benzene affords {(dtbpe)Ni}2(
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2:2-C6H6)(4). The reaction of either 2 or 4 with hydrogen (H2, HD, D2) gives {(dtbpe)Ni}2(-H)2 (3) andthe isotopomers {(dtbpe)Ni}2(-H)(-D) (3-d) and {(dtbpe)Ni}2(-D)2 (3-d2). According to theNMR spectra, the structure of 3 is dynamic in solution. The crystal structures of 2 and 3have been determined by X-ray crystallography. Solution thermolysis of 2 or reduction of(dtbpe)NiCl2 with Mg* in the presence of alkanes probably involves 
-complex-typeintermediates [(dtbpe)Ni(2-R'H)] (R' = e.g. C2H5, A). While the nonisolated [(dtbpe)Ni0]-complexes A are exceedingly reactive intermediates, isolated 3 and 4 represent easy tohandle starting complexes for [(dtbpe)Ni0] reactions. Partial protolysis of 2 with CF3SO3Haffords (dtbpe)Ni(CH3)(OSO2CF3) (5). Complex 5 reacts slowly with 2 equiv of ethene to giveequimolar amounts of [(dtbpe)Ni(C2H5)]+(OSO2CF3-) (6) and propene. The reaction is thoughtto be initiated by an insertion of ethene into the Ni-CH3 bond of 5 to form the intermediate[(dtbpe)Ni(C3H7)(OSO2CF3)] (G), followed by elimination of propene to give the hydrideintermediate [(dtbpe)Ni(H)(OSO2CF3)] (H), which on insertion of ethene into the Ni-H bondaffords 6.
-2:2-C6H6)(4). The reaction of either 2 or 4 with hydrogen (H2, HD, D2) gives {(dtbpe)Ni}2(-H)2 (3) andthe isotopomers {(dtbpe)Ni}2(-H)(-D) (3-d) and {(dtbpe)Ni}2(-D)2 (3-d2). According to theNMR spectra, the structure of 3 is dynamic in solution. The crystal structures of 2 and 3have been determined by X-ray crystallography. Solution thermolysis of 2 or reduction of(dtbpe)NiCl2 with Mg* in the presence of alkanes probably involves -complex-typeintermediates [(dtbpe)Ni(2-R'H)] (R' = e.g. C2H5, A). While the nonisolated [(dtbpe)Ni0]-complexes A are exceedingly reactive intermediates, isolated 3 and 4 represent easy tohandle starting complexes for [(dtbpe)Ni0] reactions. Partial protolysis of 2 with CF3SO3Haffords (dtbpe)Ni(CH3)(OSO2CF3) (5). Complex 5 reacts slowly with 2 equiv of ethene to giveequimolar amounts of [(dtbpe)Ni(C2H5)]+(OSO2CF3-) (6) and propene. The reaction is thoughtto be initiated by an insertion of ethene into the Ni-CH3 bond of 5 to form the intermediate[(dtbpe)Ni(C3H7)(OSO2CF3)] (G), followed by elimination of propene to give the hydrideintermediate [(dtbpe)Ni(H)(OSO2CF3)] (H), which on insertion of ethene into the Ni-H bondaffords 6.