Efficient Synthesis and Multisite Reactivity of a Phosphinidene-Bridged Mo-Re Complex. A Platform Combining...

The heterometallic complex [MoReCp(μ-PR*)(CO)₆] (3) was prepared in 60% overall yield from syn-[MoCp(PHR*)(CO)₂] via a three-step procedure involving complexes syn-[MoCp(PClR*)(CO)₂] and [MoReCp(μ-PR*)(CO)₇] as intermediate species (R* = 2,4,6-C₆H₂Bu₃). The PR* ligand in 3 displays a novel asymmetric interaction with the dimetal center, involving a double bond with one atom (Mo) and a dative single bond with the other one (Re). Compound 3 underwent thermal isomerization involving a C-H bond cleavage to yield the hydride [MoReCp(μ-H){μ-P(CH₂CMe₂)C₆H₂Bu₂}(CO)₆] and reacted with I₂ to give [MoReCpI₂(μ-PR*)(CO)₆], which displays a symmetrical phosphinidene bridge. Its reaction with methyl propiolate at 293 K proceeded with [2 + 2] cycloaddition of the alkyne and decarbonylation to yield the phosphapropenylidene-bridged complex [MoReCp{μ-κ²_P,C:η³-PR*CHC(CO₂Me)}(CO)₅] as the major product, whereas its reaction with excess CN(4-C₆H₄OMe) at 273 K proceeded with formal [2 + 1] cycloaddition of the isocyanide and further isocyanide addition at the Re site to yield the complex [MoReCp{μ-η²_P,C:κ¹_P-PR*CN(4-C₆H₄OMe)}(CO)₆{CN(4-C₆H₄OMe)}], which displays an azaphosphaallene ligand in a novel bridging coordination mode.