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American Chemical Society, Inorganic Chemistry, 15(46), p. 6091-6098, 2007

DOI: 10.1021/ic700619g

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A Theoretical Study on the Mechanism of Boron Metathesis

Journal article published in 2007 by Susmita De, Pattiyil Parameswaran ORCID, Eluvathingal D. Jemmis ORCID
This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

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Abstract

The mechanism of the boron metathesis reaction of the transition-metal-aminoborylene complex $Cp(CO)_2FeBN- (CH_3)_2 + (8)$ with EX, where $EX=H_3PO (9ap)$, $H_3AsO (9bp), H_3PS (9aq), H_3AsS (9bq)$, $CH_3CHCH_2 (9cr), (NH_2)_2- CCH_2 (9dr), H_2CO (9ep)$, and $(NH_2)_2CO (9dp)$ 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 $σ$ 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.