title: Spontaneous Si-C bond cleavage in (TriphosSi)-nickel complexes.
abstract: Herein, we report on the versatile reactions of CH3C(CH2PPh2)3as well as CH3Si(CH2PPh2)3derived 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.
authors.affiliation: Ruhr University Bochum, Inorganic Chemistry I, Universitätsstraße 150, 44801 Bochum, Germany. ulf.apfel@rub.de.
authors.forename: Anette
authors.initials: A
authors.lastname: Petuker
authors.affiliation: Freie Universität Berlin, Department of Physics, Arnimallee 14, 14195 Berlin, Germany. michael.haumann@fuberlin.de.
authors.forename: Stefan
authors.initials: S
authors.lastname: Mebs
authors.affiliation: Freie Universität Berlin, Department of Physics, Arnimallee 14, 14195 Berlin, Germany. michael.haumann@fuberlin.de.
authors.forename: Nils
authors.initials: N
authors.lastname: Schuth
authors.affiliation: Ruhr University Bochum, Inorganic Chemistry I, Universitätsstraße 150, 44801 Bochum, Germany. ulf.apfel@rub.de.
authors.forename: Philipp
authors.initials: P
authors.lastname: Gerschel
authors.affiliation: Ruhr University Bochum, Inorganic Chemistry I, Universitätsstraße 150, 44801 Bochum, Germany. ulf.apfel@rub.de.
authors.forename: Matthew L
authors.initials: ML
authors.lastname: Reback
authors.affiliation: Ruhr University Bochum, Inorganic Chemistry I, Universitätsstraße 150, 44801 Bochum, Germany. ulf.apfel@rub.de.
authors.forename: Bert
authors.initials: B
authors.lastname: Mallick
authors.affiliation: Max-Planck-Institut für chemische Energiekonversion, Stiftstrasse 34-36, 45470 Mülheim a. d. Ruhr, Germany. maurice.vangastel@cec.mpg.de.
authors.forename: Maurice
authors.initials: M
authors.lastname: van Gastel
authors.affiliation: Freie Universität Berlin, Department of Physics, Arnimallee 14, 14195 Berlin, Germany. michael.haumann@fuberlin.de.
authors.forename: Michael
authors.initials: M
authors.lastname: Haumann
authors.affiliation: Ruhr University Bochum, Inorganic Chemistry I, Universitätsstraße 150, 44801 Bochum, Germany. ulf.apfel@rub.de.
authors.forename: Ulf-Peter
authors.identifier: http://orcid.org/0000-0002-1577-2420
authors.initials: UP
authors.lastname: Apfel