Coordination Chemistry of Cyclic Disilylated Stannylenes to d10-Transition Metal Complexes

Henning Arp, Christoph Marschner*, Judith Baumgartner, Thomas Müller, Patrick Zark

*Korrespondierende/r Autor/-in für diese Arbeit

Publikation: Beitrag in einer FachzeitschriftArtikelBegutachtung

Abstract

The coordination behavior of disilylated stannylenes toward zerovalent group 10 transition metal complexes was studied. This was accomplished by reactions of PEt3 adducts of disilylated stannylenes with zerovalent group 10 transition metal complexes. The thus obtained products differed between the first row example nickel and its heavier congeners. While with nickel stannylene complex formation was observed, coordination of the stannylenes to palladium and platinum compounds led to unusual silastannene complexes of these metals. A computational model study indicated that in each case metal stannylene complexes were formed first and that the disilylstannylene/silastannene rearrangement occurs only after complexation to the group 10 metal. The isomerization is a two-step process with relatively small barriers, suggesting a thermodynamic control of product formation. In addition, the results of the computational investigation revealed a subtle balance of steric and electronic effects, which determines the relative stability of the metalastannylene complex relative to its silastannene isomer. In the case of cyclic disilylstannylenes, the Pd(0) and Pt(0) silastannene complexes are found to be more stable, while with acyclic disilylstannylenes the Ni(0) stannylene complex is formed preferentially.
Originalspracheenglisch
Seiten (von - bis)7949-7959
FachzeitschriftJournal of the American Chemical Society
Jahrgang135
DOIs
PublikationsstatusVeröffentlicht - 2013

Fields of Expertise

  • Advanced Materials Science

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