Abstract
Interaction of [Me3NH][7,8-CH2OCH2-7,8-C2B9H10] with M(NR2)4 gave the simple amine elimination products [η5-(CH2OCH2)C2B9H9]M(NMe2)2(NHMe2) (M = Zr (2a), Hf (2b)) or the unexpected C−O bond cleavage products [σ:η1:η5-(OCH2)(Me2NCH2)C2B9H9]Ti(NR2) (R = Me (3a), Et (3b)). The higher oxophilicity of the Ti center provides the driving force for the latter reactions. It is suggested that the C−O bond cleavage is prior to the amine elimination in the formation of 3a,b. This serves as a convenient and practical method for the preparation of constrained-geometry half-sandwich metallacarboranes with two different functional sidearms. Complex 3a can undergo a clean amine exchange reaction to produce new constrained-geometry titanacarborane amides. Reactions of 3a with unsaturated molecules CyNCNCy, SCS, Xyl−NC, PhC⋮N, BunNCS, Ph2CCO, and PhNCO gave monoinsertion products. They, except for [σ:η1:η5-(OCH2)(Me2NCH2)C2B9H9]Ti[η3-CyNC(NMe2)NCy] (7), do not react with amines. In sharp contrast, 7 can react readily with M...
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