Carbon monoxide formation from trimethylamine-boranecarboxylate: DFT studies of Si and chelotropic mechanisms.

Trimethylamine-boranecarboxylic acid (CH)N-BHCOOH and other amine carboxyboranes have been observed to undergo slow decarbonylation in neutral aqueous solution. This reaction, when it occurs , may have a therapeutic effect by delivering low concentrations of carbon monoxide over an extended period. In order to identify a possible mechanistic pathway for decarbonylation, the smallest tertiary amine derivative and its corresponding carboxylate ion were studied using CCSD(T)/PCM/6-311++G(2d,p)//M06-2X/PCM/6-311++G(2d,p) model chemistry. The proposed mechanistic pathway begins with a trimethylamine boranecarboxylate ion, which first undergoes an internal substitution reaction (Si) to give free amine and the carboxyborane anion BHCOO. The latter cyclic ion then releases CO a rapid chelotropic fragmentation. The role of water solvent in these reactions was explored by structural and energetic analysis of hydrogen-bonded complexes. It was found that complexation with water inhibits dissociation of trimethylamine by stabilizing the trimethylamine carboxyborane anion, whereas water accelerates CO loss by stabilizing the polar chelotropic transition state.