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Issue 44, 2018
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Cyclometallation of a germylene ligand by concerted metalation–deprotonation of a methyl group

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Abstract

The reaction of [CH{(CMe)(2,6-iPr2C6H3N)}2]GeCl with LiN(SiMe3)2 was previously reported, which led to the formation of a hetero-fulvene type germylene, [CH{(CMe)(C[double bond, length as m-dash]CH2)(2,6-iPr2C6H3N)}2]Ge through the deprotonation of the C–H bond from the methyl substituents. In this paper, we attempted the analogous reaction with (Dipp)NCMeCHCOMeGeCl using LiN(SiMe3)2 which gave rise to a metathesis product, (Dipp)NCMeCHCOMeGeN(SiMe3)2 (2). However, the reactions of 2 with [M2Cl2(μ-Cl)25-Cp*)2] (M = Rh and Ir) resulted in cyclometallated Rh and Ir complexes through the activation of the C–H bond from the germylene ligand. The complexes were characterized by single crystal X-ray analysis, which authenticated the presence of Ge–Rh and Ge–Ir bonds. DFT studies have been performed to understand the mechanism.

Graphical abstract: Cyclometallation of a germylene ligand by concerted metalation–deprotonation of a methyl group

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Publication details

The article was received on 03 Aug 2018, accepted on 05 Oct 2018 and first published on 08 Oct 2018


Article type: Paper
DOI: 10.1039/C8DT03166E
Citation: Dalton Trans., 2018,47, 15835-15844
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    Cyclometallation of a germylene ligand by concerted metalation–deprotonation of a methyl group

    K. Bakthavachalam, S. Dutta, A. C., B. Raghavendra, A. Haridas, S. S. Sen, D. Koley and S. Ghosh, Dalton Trans., 2018, 47, 15835
    DOI: 10.1039/C8DT03166E

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