A Bridging Side-on Allenylidene Dimolybdenum Complex without Carbonyl Stabilization

Abstract

International audienceThe bis(nitrile) complex [Mo2Cp2(μ-SMe)3(NCCH3)2](BF4) (1) reacts with HC⋮CCPh2(OH) to give the μ-alkyne product [Mo2Cp2(μ-SMe)3{HC⋮CCPh2(OH)}](BF4) (2). Sequential treatment with triethylamine and tetrafluoroboric acid converts 2 almost quantitatively, via the μ-alkynyl derivative 3, into [Mo2Cp2(μ-SMe)3(μ-η1:η2-CCCPh2)] (BF4) (4), the first example of a dinuclear μ-η1:η2-allenylidene species without carbonyl ligands

Synthesis and Structural Characterization of a Series of New Chiral‐at‐Metal Ruthenium Allenylidene Complexes

“…Since then, a variety of allenylidene complexes have been synthesized and characterized. The majority of allenylidene complexes are based on ruthenium,4 but other metals have been used as well, for example, Cr and W,5a Mo,5b Mn,2b Re,5c Ir,5d Rh,1f Fe,5e Os,5f,5g Pd,5h,5i and Ni 6…”

Reactions of Propargyl Compounds Containing a Cyclobutyl Group Induced by a Ruthenium Complex

“…5 The majority of transition‐metal allenylidene complexes are based on ruthenium. However, other metals, such as osmium,6a molybdenum,6b and tungsten,6c have also been reported to give similar complexes. The formation of the allenylidene complex generally proceeds by dehydration of a γ‐hydroxyvinylidene intermediate.…”

Reactivity of the metal–cyclopentadienyl (indenyl, fluorenyl and cycloheptatrienyl) bonds

“…Recently, Schollhammer's group examined the reaction of thiolato-bridged binuclear molybdenum complexes [Mo 2 Cp 2 L 2 (l-SMe) 3 ](BF 4 ) (L = XylNC, CO, Bu t ) with a base and anionic reagents, and found that the regioselectivity of nucleophilic reaction remarkably depends on the nature of the co-ligands and anionic reagents [39][40][41]. When L is a good p-acceptor, the anion attacks at the carbon atoms of the Cp favorably, leading to the occurrence of the regioselective protonation or alkylation of the Cp ligand.…”