Dehydrocoupling of dimethylamine borane by titanocene: elucidation of ten years of inconsistency between theoretical and experimental descriptions

Physical Chemistry Chemical Physics : PCCP
Jingwen ZhuMohammad Esmail Alikhani

Abstract

More than ten years ago, Manners and coworkers published the first experimental study on the efficiency of titanocene to catalyze the dehydrocoupling of dimethylamine borane (DMAB, T. Clark, C. Russell and I. Manners, J. Am. Chem. Soc., 2006, 128, 9582-9583). Several experimental investigations have shown that a two-step mechanism leads to the formation of a cyclic diborazane (Me2N-BH2)2via the linear diborazane (HNMe2-BH2-NMe2-BH3). This finding stood in contradiction to the following theoretical investigations of the reaction pathway. Herein, using dispersion-corrected density functional theory (DFT-D), we propose an energetically favored reaction mechanism in perfect agreement with the experimental findings. It is shown that van der Waals interactions play a prominent role in the reaction pathway. The formation of 3-center 2-electron interactions, classical dihydrogen bonds, and non-classical dihydrogen bonds was identified with the help of topological and localized orbital approaches.

References

Jul 27, 2006·Journal of the American Chemical Society·Timothy J ClarkIan Manners
Nov 15, 2006·Chemistry : a European Journal·Timothy J ClarkIan Manners
Aug 2, 2007·Chemical Communications : Chem Comm·Doris PunPaul J Chirik
Mar 25, 2010·The Journal of Chemical Physics·Giovanni Scalmani, Michael J Frisch
Aug 3, 2010·Chemical Reviews·Anne StaubitzIan Manners
Mar 4, 2011·Journal of Computational Chemistry·Stefan GrimmeLars Goerigk
Aug 20, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Ulf RydeStefan Grimme
Jan 31, 2012·Chemical Communications : Chem Comm·David J WolstenholmeG Sean McGrady
Apr 4, 2013·Chemical Society Reviews·Rory Waterman
Aug 22, 2013·Physical Chemistry Chemical Physics : PCCP·Stefan Grimme, Marc Steinmetz
Feb 18, 2014·Journal of the American Chemical Society·James R VanceIan Manners
Mar 12, 2015·Physical Chemistry Chemical Physics : PCCP·Emilie-Laure ZinsM Esmaïl Alikhani
Apr 29, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·David J WolstenholmeG Sean McGrady
Aug 11, 2015·Chemical Society Reviews·Rebecca L Melen
Nov 12, 2013·Journal of Chemical Theory and Computation·Yuanyuan Sun, Hui Chen
Apr 15, 2016·Chemical Reviews·Andrea Rossin, Maurizio Peruzzini

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Software Mentioned

Gaussian
NBO
QTAIM
Gaussian09
TopMod
AIMAll

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