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Reactions of a series of unsymmetrically substituted N-heterocyclic carbene ligands with Ru3(CO)12afforded a variety of mononuclear (1, 2), trinuclear (3, 4, 5, and 5′), and tetranuclear (6, 7) ruthenium complexes via intramolecular ruthenium-mediated sp2and sp3C–H bond activations. Complexes 6and 7include an octahedral cluster skeleton consisting of four ruthenium atoms and two metalated carbon atoms. The formation of this type of ruthenium clusters is proposed to involve the initial C–C double-bond migration and subsequent sp2C–H bond activations. All new complexes were fully characterized, and the molecular structures of 1, 2, 5, 6, and 7were determined by X-ray diffraction analysis. [ABSTRACT FROM AUTHOR]

Thermal treatment of Ru3(CO)12with equimolar amounts of (1H-inden-3-yl)diphenylphosphine and (1H-inden-2-yl)diphenylphosphine in octane gave two isomeric trinuclear ruthenium clusters Ru3(μ2-H)(μ3-3-Ph2PC9H6)(CO)9(1) and Ru3(μ2-H)(μ3-2-Ph2PC9H6)(CO)9(2), respectively, via a C−H bond cleavage. Heating either 1or 2in octane afforded the trinuclear and tetranuclear ruthenium clusters Ru3(μ3-PPh)(μ3-C9H6)(CO)9(3) and Ru4(μ4-PPh)(μ4-C9H6)(CO)11(4) via double C−P bond cleavage. Thermal treatment of Ru3(CO)12with (4,7-dimethyl-1H-inden-3-yl)diphenylphosphine in octane gave trinuclear ruthenium cluster Ru3(μ2-H)(μ3-3-Ph2PC11H10)(CO)9(5) via a C−H bond cleavage. Heating 5in octane afforded a trinuclear ruthenium cluster Ru3(μ3-PPh)(μ3-C11H10)(CO)9(6) and two isomeric tetranuclear ruthenium clusters Ru4(μ3-PPh)(μ2-η5:η1-C11H10)(CO)11(7) and [Ru4(μ4-PPh)(μ4-C11H10)(CO)11] (8) via double C−P bond cleavage. Thermal treatment of Ru3(CO)12with (3,4,7-trimethyl-1H-inden-1-yl)diphenylphosphine in toluene afforded two trinuclear ruthenium clusters Ru3(μ2-H)2(μ3-3-Ph2PC12H11)(CO)8(9) via both sp3and sp2C−H bond cleavage and Ru3(μ2-PPh2)(μ3-η2:η2:η5-C12H13)(CO)6(10) via a C−P bond cleavage. Thermal treatment of Ru3(CO)12with (3-methyl-1H-inden-1-yl)diphenylphosphine in toluene afforded a trinuclear ruthenium cluster Ru3(μ2-H)(μ3-3-Ph2PC10H8)(CO)9] (11) via a C−H bond cleavage. The molecular structures of complexes 1−5and 7−11have been determined by single-crystal X-ray diffraction analysis. [ABSTRACT FROM AUTHOR]