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Carbene-Bound Borane and Silane Adducts: A Comprehensive DFT Study on Their Stability and Propensity for Hydride-Mediated Ring Expansion

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journal contribution
posted on 11.11.2013, 00:00 by Mohammad R. Momeni, Eric Rivard, Alex Brown
The stability of a variety of borane (BH3 and BH2NHMe) and silane (SiHnPh4–n, n = 0–4) adducts with diamino (NHC) and aminoalkyl (CAAC) carbenes has been carefully examined using M06-2X/cc-pVDZ computations, including natural bond orbital and atoms-in-molecules analyses. Moreover a potential mechanism for the hydride-mediated ring expansion of the carbene donors is reported. While the NHC adducts can undergo thermally induced ring-expansion chemistry, the CAAC adducts show increased stability due to a large energetic barrier for the insertion of boron (or silicon) atoms into the CAAC heterocycle. A series of substituted NHCs were investigated to further explore the roles of both electronic and steric effects on adduct stabilities and on their propensities for undergoing ring-expansion transformations.

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