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Spontaneous Si–C bond cleavage in (Triphos<sup>Si</sup>)-nickel complexes

DOIFull Paper Access

21

Citations

55

References

2016

Year

Anette Petuker, Stefan Mebs, Nils Schuth, Philipp Gerschel, Matthew L. Reback, Bert Mallick, Maurice van Gastel, Michael Haumann, Ulf‐Peter Apfel
Dalton Transactions

Abstract

Herein, we report on the versatile reactions of CH<sub>3</sub>C(CH<sub>2</sub>PPh<sub>2</sub>)<sub>3</sub> as well as CH<sub>3</sub>Si(CH<sub>2</sub>PPh<sub>2</sub>)<sub>3</sub> derived Ni-complexes. While Ni[CH<sub>3</sub>C(CH<sub>2</sub>PPh<sub>2</sub>)<sub>3</sub>] complexes reveal high stability, the Ni[CH<sub>3</sub>Si(CH<sub>2</sub>PPh<sub>2</sub>)<sub>3</sub>] analogs show rapid decomposition at room temperature and afford the unprecedented pseudo-tetrahedral phosphino methanide complex 5. We provide a detailed electronic structure of 5 from X-ray absorption and emission spectroscopy data analysis in combination with DFT calculations, as well as from comparison with structurally related complexes. A mechanistic study for the formation of complex 5 by reaction with BF<sub>4</sub><sup>-</sup> is presented, based on a comparison of experimental data with quantum chemical calculations. We also show a simple route towards isolable Ni(i)-complexes on the gram scale.

References

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