A theoretical study on the mechanism of boron metathesis

De, Susmita ; Parameswaran, Pattiyil ; Jemmis, Eluvathingal D. (2007) A theoretical study on the mechanism of boron metathesis Inorganic Chemistry, 46 (15). pp. 6091-6098. ISSN 0020-1669

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Official URL: http://pubs.acs.org/doi/abs/10.1021/ic700619g

Related URL: http://dx.doi.org/10.1021/ic700619g


The mechanism of the boron metathesis reaction of the transition-metal-aminoborylene complex Cp(CO)2FeBN(CH3)2+ (8) with EX, where EX = H3PO (9ap), H3AsO (9bp), H3PS (9aq), H3AsS (9bq), CH3CHCH2 (9cr), (NH2)2CCH2 (9dr), H2CO (9ep), and (NH2)2CO (9dp) is investigated at the B3LYP/LANL2DZ level. The analysis of bonding and charge distribution shows that the Fe-borylene complex (8) is a Fischer-type carbene analogue. The attack of the olefin takes place at the metal end of the M=C bond of the metal-carbene complex in olefin metathesis and proceeds via [2 + 2] cycloaddition, while in boron metathesis, the initial attack of the substrates takes place at the positively charged B atom of the Fe-borylene complex and forms the preferred acyclic intermediate. The energetics of boron metathesis is comparable to that of the olefin metathesis. Substrates that are polar and a have low-lying σ molecular orbital (weak s bond) prefer the boron metathesis reaction. The relative stability of the metathesis products is controlled by the strength of the Fe-E and B-X bonds of the products 13 and 14, respectively. We have also investigated the possibility of a β-hydride-transfer reaction in the Fe-borylene complex.

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