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A Bis(silylenyl)pyridine Zero-Valent Germanium Complex and Its Remarkable Reactivity

A Bis(silylenyl)pyridine Zero-Valent Germanium Complex and Its Remarkable Reactivity

Yu-Peng Zhou, Miriam Karni, Shenglai Yao, Yitzhak Apeloig, Matthias Driess

Angew Chem Int Ed Engl. 2016 Nov 21;55(48):15096-15099.

PMID: 27804223

Abstract:

The synthesis, reactivity, and electronic structure of the unique germylone iron carbonyl complex [SiNSi]Ge0 →Fe(CO)4 is reported. The compound was obtained in 49 % yield from the reaction of the bis(N-heterocyclic silylenyl)pyridine pincer ligand SiNSi (1,6-C5 NH3 -[EtNSi(Nt Bu)2 CPh]2 ) with GeCl2 ⋅(dioxane) to give the corresponding chlorogermyliumylidene chloride precursor [SiNSi]GeII Cl+ Cl- , which was further reduced with K2 Fe(CO)4 . Single-crystal X-ray diffraction analysis of [SiNSi]Ge→Fe(CO)4 revealed that the Ge0 center adopts a trigonal-pyramidal geometry with a Si-Ge-Si angle of 95.66(2)°. Remarkably, one of the SiII donor atoms in the complex is five-coordinated because of additional (pyridine)N→Si coordination. Unexpectedly, the reaction of [SiNSi]Ge→Fe(CO)4 with GeCl2 ⋅(dioxane) (one molar equivalent) yielded the first push-pull germylone-germylene donor-acceptor complex, [SiNSi]Ge→GeCl2 →Fe(CO)4 through the insertion of GeCl2 into the dative Ge0 →Fe bond. The electronic features of the new compounds were investigated by DFT calculations.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP28595677	Germanium(II) chloride dioxane complex (1:1)		28595-67-7	Price

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