Ring Expansion of Cyclic Triplatinum(0) Silylene Complexes
Induced by Insertion of Alkyne into a Si–Pt Bond
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Abstract
Triangular triplatinum(0) complexes
with bridging diarylsilylene ligands, [{Pt(PMe<sub>3</sub>)}<sub>3</sub>(μ-SiAr<sub>2</sub>)<sub>3</sub>] (<b>1</b>: Ar = Ph, <b>2</b>: Ar = C<sub>6</sub>H<sub>4</sub>F-4), reacted with dimethyl
acetylenedicarboxylate to afford new Pt<sub>3</sub> complexes. The
equimolar reaction of complex <b>1</b> produced a linear triplatinum
complex with μ<sub>2</sub>-diphenylsilylene and μ<sub>3</sub>-phenyl(vinylene)silylene ligands. The latter ligand was formed
via migration of a Ph group of the bis(diphenylsilyl)ethylene ligand.
The reaction of <b>2</b> with the alkyne in a 1:3 molar ratio
yielded the product having a disilaplatinacyclic moiety and a Pt center
with the donor-stabilized silylene ligand, and they were separated
by the coordinated alkyne molecule. A common intermediate having a
disilaplatinacyclopentene group was converted into the respective
triplatinum complexes, depending on the substituents of the silylene
ligand
