Reactivity of Diynes with a 1-Azavinylidene-Bridged Triruthenium Carbonyl Cluster. Insertion Reactions of Diynes into Ru−H, Ru−C, and Ru−N Bonds

The reactivity of the 1-azavinylidene cluster complex [Ru3(μ-H)(μ-NCPh2)(CO)10] (1) with diynes has been studied. The nonconjugated diyne 1-trimethylsilyl-1,4-pentadiyne affords the binuclear ynenyl derivative [Ru2(μ-NCPh2)(μ-η2-CH2CCH2C⋮CSiMe3)(CO)6] (2), which results from cluster fragmentation and from the insertion of the terminal alkyne fragment of the diyne into a Ru−H bond. The reactions of 1 with the internal conjugated diynes 1,6-diphenoxy-2,4-hexadiyne, 2,4-hexadiyne, and diphenylbutadiyne have allowed the isolation of the trinuclear derivatives [Ru3{μ-η2-NCPh(C6H4)}(μ3-η4-PhOCH2CHCCCHCH2OPh)(CO)8] (3), [Ru3{μ3-η4-NCPh(C6H4)CH(Me)CHCCMe}(CO)9] (4), [Ru3{μ-η2-NCPh(C6H4)}(μ3-η4-PhCHCHC⋮CPh)(CO)8] (5), and [Ru3{μ3-η4-PhCHCHC(CPh)NCPh(C6H4)}(CO)9] (6). The four compounds have been characterized by X-ray diffraction methods. They all arise from the orthometalation of a phenyl ring of the 1-azavinylidene ligand and from the transfer of two hydride ligands (the original plus that coming from the orthom...