η3-silaallyl/alkenylsilyl molybdenum complex: Synthesis, structure, and reactivity toward primary amines to form Mo-N-Si three-membered cyclic complexes

Hiroyuki Sakaba, Hiroki Tonosaki, Kazuyoshi Isozaki, Eunsang Kwon

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4 Citations (Scopus)

Abstract

The new η3-silaallyl/alkenylsilyl molybdenum complex Cp∗Mo(CO)23-Ph2SiCHCMe2) (3) was synthesized by the reaction of Cp∗Mo(CO)2(py)Me with Ph2HSiCH-CMe2. Reactions of 3 with primary amines RNH2 (R = tBu, iPr, Et) gave Mo-N-Si three-membered cyclic complexes Cp∗Mo(CO)22-N,Si-RHNSiPh2) (5a, R = tBu; 5b, R = iPr; 5c, R = Et) with elimination of isobutene. In NMR tube reactions using iPrNH2 and EtNH2, the Mo-N-Si-C four-membered cyclic complexes Cp∗Mo(CO)22-N,C-RHNSiPh2CHiPr) (4b, R = iPr; 4c, R = Et) were observed as intermediates leading to 5b and 5c, respectively. Complex 4c was successfully isolated in a preparative reaction. The molecular structures of 3, 4c, and 5b were determined by X-ray crystal analyses. Interestingly, the contribution of silylene character was suggested for the SiPh2 moiety of 5b from the X-ray structure. The reaction of 5b with MeOH gave the dinuclear complex Cp∗(CO)2Mo(η-OMe)(η -H)Mo(CO)2Cp∗ as a major product.

Original languageEnglish
Pages (from-to)1029-1037
Number of pages9
JournalOrganometallics
Volume34
Issue number6
DOIs
Publication statusPublished - 2015 Mar 23

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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