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Issue 8, 2010
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Reactions of a hydrido(hydrogermylene)tungsten complex with some heterocumulenes: hydrogermylation and thermal rearrangement

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Abstract

Reaction of a hydrido(hydrogermylene)tungsten complex Cp*(CO)2(H)W[double bond, length as m-dash]Ge(H)[C(SiMe3)3] (1) with isocyanate PhNCO at room temperature resulted in stoichiometric hydrogermylation at the C[double bond, length as m-dash]O bond to give a W–Ge–O–C–N five-membered chelate complex. In contrast, the reactions of 1 with isothiocyanates RNCS (R = Ph, Me) led to hydrogermylation at the C[double bond, length as m-dash]N bond to yield W–Ge–N–C–S five-membered chelate complexes. In both cases, the most electronegative atom in the isocyanate or isothiocyanates attacks the germanium of 1. Gentle heating of the latter chelate complexes in hydrocarbon solvents caused rearrangement of the chelate ring to cleanly afford W–Ge–S–C–N chelate complexes. Molecular structures of these three different types of five-membered metallacycles have been determined by X-ray crystallography, and possible reaction mechanisms for the hydrogermylation and rearrangement reactions have been proposed.

Graphical abstract: Reactions of a hydrido(hydrogermylene)tungsten complex with some heterocumulenes: hydrogermylation and thermal rearrangement

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Article information


Submitted
19 Feb 2010
Accepted
30 Apr 2010
First published
10 Jun 2010

New J. Chem., 2010,34, 1723-1730
Article type
Paper

Reactions of a hydrido(hydrogermylene)tungsten complex with some heterocumulenes: hydrogermylation and thermal rearrangement

H. Hashimoto, T. Fukuda and H. Tobita, New J. Chem., 2010, 34, 1723
DOI: 10.1039/C0NJ00137F

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