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J Am Chem Soc. 2009 Mar 18;131(10):3493-8. doi: 10.1021/ja809892a.

2-Indenylidene pincer complexes of zirconium and palladium.

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  • 1Université de Toulouse, UPS, Laboratoire Hétérochimie Fondamentale et Appliquée, 118 route de Narbonne, F-31062 Toulouse, France.


[IndH(2)(Ph(2)P=X)(2)] derivatives (1, X = NMes; 4, X = S) react with [Zr(NMe(2))(4)] and [PdCl(2)(cod)] to afford the complexes {[Ind(Ph(2)PNMes)(2)]Zr(NMe(2))(2)} (3), {[Ind(Ph(2)PS)(2)]Zr(NMe(2))(2)} (5), and {[Ind(Ph(2)PS)(2)]Pd(HNc-Hex(2))} (7). The ability of the phosphazene and thiophosphinoyl side arms to support the coordination of the indenyl ring as 2-indenylidene was evidenced by NMR spectroscopy and X-ray diffraction studies. Analysis of the bonding situation by density functional theory calculations revealed a strong sigma interaction but a negligible (if any) pi interaction between C2 and the metal.

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