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Issue 3, 2017
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Spontaneous Si–C bond cleavage in (TriphosSi)-nickel complexes

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Abstract

Herein, we report on the versatile reactions of CH3C(CH2PPh2)3 as well as CH3Si(CH2PPh2)3 derived Ni-complexes. While Ni[CH3C(CH2PPh2)3] complexes reveal high stability, the Ni[CH3Si(CH2PPh2)3] 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 BF4 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.

Graphical abstract: Spontaneous Si–C bond cleavage in (TriphosSi)-nickel complexes

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Publication details

The article was received on 21 Oct 2016, accepted on 08 Dec 2016 and first published on 08 Dec 2016


Article type: Paper
DOI: 10.1039/C6DT04048A
Dalton Trans., 2017,46, 907-917
  • Open access: Creative Commons BY license
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    Spontaneous Si–C bond cleavage in (TriphosSi)-nickel complexes

    A. Petuker, S. Mebs, N. Schuth, P. Gerschel, M. L. Reback, B. Mallick, M. van Gastel, M. Haumann and U. Apfel, Dalton Trans., 2017, 46, 907
    DOI: 10.1039/C6DT04048A

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