Abstract
Herein we report on the reactions of the stable LSiCl (1) and LGeCl (2) [L = PhC(NtBu)(2)] with L(1)Ge, [L(1) = CH{(C[double bond, length as m-dash]CH(2))(CMe)(2,6-iPr(2)C(6)H(3)N)(2)}] (3) to yield 1-sila-5-germylene (4) and a 1,5-bis(germylene) (5). The reactions proceed through the 1,4 nucleophilic addition of the M-Cl (M = Si or Ge) to 3 without any modification of the oxidation state although the change of the oxidation state is thermodynamically more favorable. Compounds 4 and 5 were investigated by single crystal X-ray structural analyses, multi-nuclear NMR spectroscopy, and micro-analysis. Treatment of L(1)AlMe·thf (6) with 1 resulted in the formation of the 1-sila-5-aluminium complex (7). The complex contains a Si(II) and an Al(III) atom in the molecule. All reported reactions proceed without changing the oxidation states at the metal centers.
Highlights
We report on the reactions of the stable LSiCl (1) and LGeCl (2) [L = PhC(NtBu)2] with L1Ge, [L1 = CH{(CQCH2)(CMe)(2,6-iPr2C6H3N)2}] (3) to yield 1-sila5-germylene (4) and a 1,5-bis(germylene) (5)
The first stable N-heterocyclic silylene was reported by West et al in 1994,1 whereas the first N-heterocyclic germylene was isolated by Veith and Grosser in 1982.2 Since a number of room temperature stable silylenes3a–f and germylenes3g–m were synthesized and structurally characterized
Considering the success that type A showed, it seemed appropriate to attempt the synthesis of type B
Summary
The synthesis of a compound where two different elements are present in low oxidation states, and each possesses a lone pair of electrons, is of prime interest. Such a goal is definitely challenging and requires a suitable precursor.[9] The prototypical approach to synthesize type B is to vary the substituents on the nitrogen atom or modify the backbone skeleton of the precursors.7a,8a these methods are not appropriate if two different centers have to be present in a single molecule both in low oxidation states.
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