119747-56-7Relevant academic research and scientific papers
A Novel Route to Vinylidene Complexes, and Metal-Induced Coupling of Two Vinylidene Units to Butatriene Complexes
Schubert, Ulrich,Groenen, Juergen
, p. 1237 - 1246 (2007/10/02)
A novel method for the synthesis of vinylidene complexes is exemplified for complexes MeCp(CO)LMn=C=CR2 (L = CO, PMePh2, P(OR')3; R = Me, Ph) and (?-Ar)(CO)2Cr=C=CR2 (?-Ar = C6H6, 1,3,5-C6H3Me3, C6Me6).These complexes are prepared by reaction of mostly photochemically generated MeCp(CO)LMn or (?-Ar)(CO)2Cr with (α-chlorovinyl)silanes, R'3SiC(Cl)=CR2.With an excess of R'3SiC(Cl)=CR2, butatriene complexes MeCp(CO)LMn(η2-R2C=C=C=CR2) or (?-Ar)(CO)2Cr(η2-R2C=C=C=CR2) are preferentially formed instead.Common precursor for both vinylidene and butatriene complexes are compounds in which the C-Cl bond of the (α-chlorovinyl)silane is oxidatively added to the metal.This precursor either yields the vinylidene complex by intramolecular chlorosilane elimination or reac6ts with a second equivalent of (α-chlorovinyl)silane to give a butatriene complex.Model reactions indicate that formation of the butatriene ligand proceeds by initial formation of a substituted butadiene ligand from two vinyl units, and subsequent chlorosilane elimination. - Key Words: Butatriene derivatives / C-C coupling, metal-induced / Silanes, (α-chlorovinyl)- / Vinylidene complexes
