Titanacarborane mediated C–N bond forming/breaking reactions

Constrained-geometry titanacarboranes [σ:η1:η5-(OCH2)(R2NCH2)C2B9H9]Ti(NR2) (R = Me, Et) are synthesized via an unexpected reaction of [Me3NH][μ-7,8-CH2OCH2-7,8-C2B9H10] with Ti(NR2)4 (R = Me, Et), involving a C–O bond cleavage and C–N bond formation. These complexes can be readily converted to new amide species or alkoxide by reacting with amines or esters, respectively. Insertion of a series of unsaturated molecules into the Ti–N bond of the aforementioned complexes results in the formation of various half-sandwich titanacarboranes. [σ:η1:η5-(OCH2)(Me2NCH2)C2B9H9]Ti(NMe2) is also able to efficiently catalyze the hydroamination of carbodiimides and the transamination of guanidines. These results are summarized in this brief account.

This brief account summarizes our very recent work on the synthesis, structure, reactivity, and catalysis of half-sandwich constrained-geometry titanacarboranes [σ:η1:η5-(OCH2)(R2NCH2)C2B9H9]Ti(NR2) (R = Me, Et).Figure optionsDownload as PowerPoint slide