Unique σ-bond metathesis of silylalkynes promoted by an ansa-dimethylsilyl and oxo-bridged uranium metallocene

Jiaxi Wang, Ylia Gurevich, Mark Botoshansky, Moris S. Eisen*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

29 Scopus citations

Abstract

The tetrachloride salt of uranium reacts with 1 equiv of the lithium ligand Li2[(C5Me4)2SiMe2] in DME to form the complex [η5-(C5Me4)2SiMe2]UCl2·2LiCl·2DME (1), which undergoes a rapid hydrolysis in toluene to yield the dimeric bridged monochloride, monooxide complex [{[η5-(C5Me4)2SiMe2]UCl}2(μ-O)(μ-Cl)•Li•1/2DME]2 (2). Metathesis of 2 with BuLi in DME gives the mono-bridged dibutyl complex {[η5-(C5Me4)2SiMe2]UBu}2(μ-O) (3). Complex 2 was characterized by solid-state X-ray analysis. Complex 3 was found to be an active catalyst for the disproportionation metathesis of TMSC≡CH (TMS = SiMe3) and the cross-metathesis of TMSC≡CH or TMSC≡CTMS with various terminal alkynes. The metathesis of TMSC≡CH gives TMSC≡CTMS and HC≡CH, whereas the cross-metathesis of TMSC≡CH or TMSC≡CTMS with terminal alkynes (RC≡CH) yields TMSC≡CTMS, TMSC≡CR, and HC≡CH. In addition, TMSC≡CCH3 also was found to react with tBuC≡CH, yielding TMSC≡CBut and CH3C≡CH. A plausible mechanism for the catalytic process is presented.

Original languageEnglish
Pages (from-to)9350-9351
Number of pages2
JournalJournal of the American Chemical Society
Volume128
Issue number29
DOIs
StatePublished - 26 Jul 2006
Externally publishedYes

Fingerprint Dive into the research topics of 'Unique σ-bond metathesis of silylalkynes promoted by an ansa-dimethylsilyl and oxo-bridged uranium metallocene'. Together they form a unique fingerprint.

Cite this