Cooperative N-H bond activation by amido-Ge(ii) cations

Xueer Zhou, Petra Vasko, Jamie Hicks, M. Ángeles Fuentes, Andreas Heilmann, Eugene L. Kolychev, Simon Aldridge*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

7 Citations (Scopus)

Abstract

N-heterocyclic carbene (NHC) and tertiary phosphine-stabilized germylium-ylidene cations, [R(L)Ge:]+, featuring tethered amido substituents at R have been synthesized via halide abstraction. Characterization in the solid state by X-ray crystallography shows these systems to be monomeric, featuring a two-coordinate C,N-or P,N-ligated germanium atom. The presence of the strongly Lewis acidic cationic germanium centre and proximal amide function allows for facile cleavage of N-H bonds in 1,2-fashion: The products resulting from reactions with carbazole feature a tethered secondary amine donor bound to a three-coordinate carbazolyl-GeII centre. In each case, addition of the components of the N-H bond occurs to the same face of the germanium amide function, consistent with a coordination/proton migration mechanism. Such as sequence is compatible with the idea that substrate coordination via the pπ orbital at germanium reduces the extent of N-to-Ge π donation from the amide, thereby enhancing the basicity of the proximal N-group.

Original languageEnglish
Pages (from-to)9495-9504
Number of pages10
JournalDalton Transactions
Volume49
Issue number27
DOIs
Publication statusPublished - 21 Jul 2020
Externally publishedYes

Fingerprint

Dive into the research topics of 'Cooperative N-H bond activation by amido-Ge(ii) cations'. Together they form a unique fingerprint.

Cite this