Journal of Organometallic Chemistry p. 129 - 137 (1997)
Update date:2022-08-04
Topics:
Walther, Dirk
Klettke, Thomas
Goerls, Helmar
Imhof, Wolfgang
(cod)2Ni reacts with Ph3Si-C≡C-CMe3 to form the mixed complex (cod)Ni(alkyne) (1), (cdt)Ni and Ph3Si-C≡C-CMe3 yield the homoleptic compound (alkyne)2Ni (2) (cod: cyclooca-1.5-diene, cdt: cyclododeca-1.5.9-triene). Both crystal structures were determined by X-ray diffraction analysis. In 2 the Ni(0) center is surrounded by the four carbon atoms of the alkynes yielding a distorted nickel-centered C4 tetrahedron (NiC4). Reaction of the alkynylsilanes Ph2Si(-C≡C-R)2 (R = CMe3, SiMe3) and of PhSi(-≡C-CMe3)2 with (cdt)Ni gives dimeric compounds of the type [(alkinylsilane)Ni(0)]2 (3-5), which have been characterized by X-ray diffraction determination. 3-5 show very similar structures in the solid state. Two silicon-centered C4 tetrahedra (SiC4) are connected with two NiC4 tetrahedra by the four carbon atoms which are related to the two different kinds of tetrahedra. This structural principle can be compared with the structure of tetrasiloxanes. According to the temperature-dependent 13C NMR spectra of 5 several conformers can be detected in solution.
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