4.7 Article

Comparison of group 4 and thorium M(IV) substituted cyclopentadienyl silanide complexes

Journal

DALTON TRANSACTIONS
Volume 52, Issue 22, Pages 7635-7645

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d3dt00987d

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We synthesized and characterized a series of M(IV) substituted cyclopentadienyl hypersilanide complexes of the formula [M(Cp-R)(2){Si(SiMe3)(3)}(X)]. The reactions of [M(Cp-R)(2)(Cl)(2)] with K{Si(SiMe3)(3)} gave mono-silanide complexes [M(Cp')(2){Si(SiMe3)(3)}(Cl)]. The complexes were characterized by XRD, NMR spectroscopy, ATR-IR spectroscopy, and density functional theory calculations.
We report the synthesis and characterisation of a series of M(IV) substituted cyclopentadienyl hypersilanide complexes of the general formula [M(Cp-R)(2){Si(SiMe3)(3)}(X)] (M = Hf, Th; CpR = Cp', {C5H4(SiMe3)} or Cp'', {C5H3(SiMe3)(2)-1,3}; X = Cl, C3H5). The separate salt metathesis reactions of [M(Cp-R)(2)(Cl)(2)] (M = Zr or Hf, CpR = Cp'; M = Hf or Th, CpR = Cp'') with equimolar K{Si(SiMe3)(3)} gave the respective mono-silanide complexes [M(Cp')(2){Si(SiMe3)(3)}(Cl)] (M = Zr, 1; Hf, 2), [Hf(Cp'')(Cp'){Si(SiMe3)(3)}(Cl)] (3) and [Th(Cp'')2{Si (SiMe3)(3)}(Cl)] (4), with only a trace amount of 3 presumably formed via silatropic and sigmatropic shifts; the synthesis of 1 from [Zr(Cp')(2)(Cl)(2)] and Li{Si(SiMe3)(3)} has been reported previously. The salt elimination reaction of 2 with one equivalent of allylmagnesium chloride gave [Hf(Cp')2{Si(SiMe3)(3)}(eta(3)-C3H5)] (5), whilst the corresponding reaction of 2 with equimolar benzyl potassium yielded [Hf(Cp')(2)(CH2Ph) 2] (6) together with a mixture of other products, with elimination of both KCl and K{Si(SiMe3)(3)}. Attempts to prepare isolated [M(CpR)(2){Si(SiMe3)(3)}](+) cations from 4 or 5 by standard abstraction methodologies were unsuccessful. The reduction of 4 with KC8 gave the known Th(III) complex, [Th(Cp'')(3)]. Complexes 2-6 were characterised by single crystal XRD, whilst 2, 4 and 5 were additionally characterised by H-1, C-13{H-1} and Si-29{H-1} NMR spectroscopy, ATR-IR spectroscopy and elemental analysis. In order to probe differences in M(IV)-Si bonds for d- and f-block metals we studied the electronic structures of 1-5 by density functional theory calculations, showing M-Si bonds of similar covalency for Zr(IV) and Hf(IV), and less covalent M-Si bonds for Th(IV).

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