Structure–reactivity correlations in new W(IV) and Nb(IV) silicon-bridged ansa-metallocene hydrides

Conway, Stephen L. J.; Green, Malcolm L. H.; Pascu, Sofia I. and Peake, Henry O. (2006). Structure–reactivity correlations in new W(IV) and Nb(IV) silicon-bridged ansa-metallocene hydrides. Polyhedron, 25(2) pp. 406–420.

DOI: https://doi.org/10.1016/j.poly.2005.08.025

Abstract

W(IV) and Nb(IV) derivatives: [W(L1)MeI] (1), [W(L1)MeH] (2) and [W(L1)O] (3), [W(L2)Cl₂] (4), [W(L2)H₂] (5), [W(L2)H₃][BF₄] (6), [Nb(L2)Cl₂] (7) and [Nb(L2)(η²-BH₄)] (8), where L1 = [(η-C₅H₄)₂SiMe₂]²⁻ and L2 = [(η-C₅H₃TMS)₂SiMe₂]²⁻, have been prepared and characterised. The crystal structures of compounds 5 and 8 have been determined. Thermodynamic parameters for the elimination of methane from compound 2 have been evaluated based on ¹H NMR studies in C₆D₆. Trimethylsilyl substituents on the cyclopentadienyl rings appear to moderate the structural and dynamic properties of the silicon-bridged ansa-tungstenocenes.

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