Reactions of (Me 2C)(Me 2Si)[(η 5-C 5H 3)Mo(CO) 3] 2 with nitrile and subsequent cleavage of the C [tbnd]N bond by cooperation of molybdenum and ruthenium

Abstract

Reaction of the doubly bridged dinuclear molybdenum complex (Me 2C)(Me 2Si)[(η 5-C 5H 3)Mo(CO) 3] 2 ( 1) with benzonitrile in refluxing xylene afforded complexes (Me 2C)(Me 2Si)[(η 5-C 5H 3) 2Mo 2(CO) 4(μ-η 2-η 2(⊥)-N CPh)] ( 2) (50%) and (Me 2C)(Me 2Si)[(η 5-C 5H 3) 2Mo 2(CO) 4(μ-η 1-η 2-N CPh)] ( 3) (6%) with different coordination of nitrile. The corresponding μ-η 2-η 2 acetonitrile and propionitrile complexes 4 and 5 could be obtained from the reactions of (Me 2C)(Me 2Si)(C 5H 4) 2 with (RCN) 3Mo(CO) 3 (R = Me, Et) in refluxing xylene. Reactions of 1 with isonitriles generated μ-η 1-η 2-C NR (R = t Bu, Ph, C 6H 11) bridged complexes 6– 8 in 53–63% yields. Subsequent reaction of 4 with Ru 3(CO) 12 yielded two C N bond cleavaged MoRu clusters (Me 2C)(Me 2Si)(η 5-C 5H 3) 2Mo 2Ru 3(CO) 10(μ-CO)(μ 3-CMe)(μ 4-N) ( 9) (7%) and [(Me 2C)(Me 2Si)(η 5-C 5H 3) 2] 2Mo 4Ru 6(CO) 16(μ-CO)(μ 4-CO) 2(μ 3-η 1-η 2-η 2-N CMe)(μ 3-CMe)(μ 5-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.