Reactions of tungsten acetylide-silylene complexes with pyridines: Direct observation of silylene/silyl migration in tungsten acetylide and carbyne/vinylidene frameworks

Hiroyuki Sakaba, Hiroyuki Oike, Yasuhiro Arai, Eunsang Kwon

Research output: Contribution to journalArticlepeer-review

11 Citations (Scopus)

Abstract

Reaction of acetylide-silylene complex Cp*(CO)2W(SiPh 2)(CCtBu) (1a) with 4-(dimethylamino)pyridine (DMAP) gave an equilibrium mixture of DMAP-stabilized silylene acetylide complexes trans- and cis-Cp*(CO)2W(SiPh2·DMAP)(CC tBu) (trans-4 and cis-4). The corresponding reaction using Cp*(CO)2W(SiPh2)(CCSiMe3) (2) produced the novel DMAP-coordinated silenylcarbyne/silylvinylidene complex Cp*(CO)2W[CC(SiPh2·DMAP)(SiMe3)] (6a) as a major product, which was equilibrated with trans- and cis-Cp*(CO)2W(SiPh2·DMAP)(CCSiMe 3) (trans-5a and cis-5a) via silylene/silyl migration. The novel structures of cis-4 and 6a were revealed by X-ray crystallography. A mixture of 2 and pyridine exhibited interesting temperature-dependent NMR spectral changes, indicating the formation of trans- and cis-Cp*(CO)2W(SiPh 2·py)(CCSiMe3) (trans-5b and cis-5b) and Cp*(CO)2W[CC(SiPh2·py)(SiMe3)] (6b) at low temperature, while a mixture of 1a and pyridine showed no such spectral changes.

Original languageEnglish
Pages (from-to)8172-8177
Number of pages6
JournalOrganometallics
Volume31
Issue number23
DOIs
Publication statusPublished - 2012 Dec 10

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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