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Published on: April 9, 2018
Osme bonds combining methyl carbon electron donation to group-8 metal σ-holes
Hangyu Zhou1, Zixuan Wang1, Qingzhong Li1
1The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University Yantai 264005 P. R. China lqz@ytu.edu.cn.
Abstract:
DFT calculations have been used to analyze the osme bonds pairing MO4 and MO3Me (M = Fe, Ru, Os) with a methyl group of BeMe2 and MgMe2. Despite lacking a formal lone pair, the methyl C atom can act as a directional and tunable electron donor. Interaction energies span the range between -7 and -23 kJ mol-1, with Fe forming the weakest and Os the strongest bonds. The replacement of one O atom of MO4 by a methyl group substantially strengthens the interaction even though it attenuates the σ-hole on M. The osme bonds are dominated by electrostatic and dispersion energies in varying amounts, but polarization plays a particularly important role for the MO3Me systems, especially for M = Fe.
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