Journal article
Ab Initio and DFT Study of Homolytic Substitution Reactions of Acyl Radicals at Silicon, Germanium, and Tin
SM Horvat, CH Schiesser
Organometallics | AMER CHEMICAL SOC | Published : 2009
DOI: 10.1021/om801016x
Abstract
Ab initio calculations using the 6-311G(d, p), cc-pVDZ, aug-cc-pVDZ, and (valence) double-pseudopotential (DZP) basis sets, with (MP2, ROMP2, QCISD, CCSD(T)) and without (HF) the inclusion of electron correlation, and density functional (BHandHLYP) calculations predict that homolytic substitution reactions of acetyl radicals at the silicon atoms in dimethylsilane can proceed via both backside and frontside attack mechanisms. At the highest level of theory (CCSD(T)/aug-cc-pVDZ//MP2/aug-ccpVDZ), energy barriers (ΔE ‡) of 110.4 and 107.5 kJ mol-1 are calculated for the backside and frontside reactions, respectively. Similar results are obtained for reactions involving germanium and tin with ene..
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Funding Acknowledgements
This work would not have been possible without the generous support of the Australian Research Council through the Centers of Excellence Program. We also gratefully acknowledge the support of the Victorian Institute for Chemical Sciences High Performance Computing Facility and the Australian Partnership for Advanced Computing.