A Diverse Array of C-C Bonds Formed at a Tantalum Metal Center.

We demonstrate the formation of a diverse array of organic and organometallic products containing newly formed C-C bonds via successive methyl transfers from di-, tri-, and tetramethyl Ta(V) precursors to unsaturated small molecule substrates under mild conditions. The reactions of Ta(V) methyl complexes - [HB(Im)]TaMeX (X = Me, Cl; Im = imidazole, Mes = 2,4,6-trimethylphenyl) with CO led to oxo enolate Ta(V) products, in which the enolate ligands were constructed from Ta-Me groups and two equivalents of CO. Similarly, the reaction of with CNXyl yielded an imido enamine Ta(V) product. Surprisingly, reacted with CNXyl (1 equiv) at the borate backbone of the [HB(Im)] ligand with concomitant methyl transfer from the metal center to form a new, dianionic scorpionate ligand that supported a Ta(V) dimethyl chloro complex (). Treatment of with further CNXyl led to an azaallyl scorpionate complex, and an imido isocyanide scorpionate complex, along with propene and xylyl ketenimine. Complex reacted with CO to yield a pinacol scorpionate complex -a new reaction pathway in early transition metal chemistry. Mechanistic studies revealed that this proceeded via migratory insertion of CO into a Ta-Me group, followed by methyl transfer to form an η-acetone intermediate. Elimination of acetone furnished a CO-stabilized Ta(III) intermediate capable of rebinding and subsequently coupling two equivalents of CO-derived acetone to form the pinacol ligand in .