Reactions of (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 with nitrile and subsequent cleavage of the CN bond by cooperation of molybdenum and ruthenium

Reaction of the doubly bridged dinuclear molybdenum complex (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 (1) with benzonitrile in refluxing xylene afforded complexes (Me2C)(Me2Si)[(η5-C5H3)2Mo2(CO)4(μ-η2-η2(⊥)-NCPh)] (2) (50%) and (Me2C)(Me2Si)[(η5-C5H3)2Mo2(CO)4(μ-η1-η2-NCPh)] (3) (6%) with different coordination of nitrile. The corresponding μ-η2-η2 acetonitrile and propionitrile complexes 4 and 5 could be obtained from the reactions of (Me2C)(Me2Si)(C5H4)2 with (RCN)3Mo(CO)3 (R = Me, Et) in refluxing xylene. Reactions of 1 with isonitriles generated μ-η1-η2-CNR (R = tBu, Ph, C6H11) bridged complexes 6–8 in 53–63% yields. Subsequent reaction of 4 with Ru3(CO)12 yielded two CN bond cleavaged MoRu clusters (Me2C)(Me2Si)(η5-C5H3)2Mo2Ru3(CO)10(μ-CO)(μ3-CMe)(μ4-N) (9) (7%) and [(Me2C)(Me2Si)(η5-C5H3)2]2Mo4Ru6(CO)16(μ-CO)(μ4-CO)2(μ3-η1-η2-η2-NCMe)(μ3-CMe)(μ5-N) (10) (8%). All the new complexes have been fully characterized. The molecular structures of 2, 4, 6, 9, and 10 have been determined by X-ray diffraction analysis.

The μ-η2-η2 nitrile complexes were obtained by thermal reaction of (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 with PhCN or from (Me2C)(Me2Si)(C5H4)2 and (RCN)3Mo(CO)3 (R = Me, Et). Subsequent reaction of the μ-η2-η2 acetonitrile complex with Ru3(CO)12 yielded two CN bond cleavaged MoRu clusters.Figure optionsDownload as PowerPoint slide