Insights into the unusual barrierless reaction between two closed shell molecules, (CH3)2S + F2, and its H2S + F2 analogue: role of recoupled pair bonding

The Journal of Physical Chemistry. a
Jeff LeidingThom H Dunning

Abstract

Early flowtube studies showed that (CH(3))(2)S (DMS) reacted very rapidly with F(2); hydrogen sulfide (H(2)S), however, did not. Recent crossed molecular beam studies found no barrier to the reaction between DMS and F(2) to form CH(2)S(F)CH(3) + HF. At higher collision energies, a second product channel yielding (CH(3))(2)S-F + F was identified. Both reaction channels proceed through an intermediate with an unusual (CH(3))(2)S-F-F bond structure. Curiously, these experimental studies have found no evidence of direct F(2) addition to DMS, resulting in (CH(3))(2)SF(2), despite the fact that the isomer in which both fluorines occupy axial positions is the lowest energy product. We have characterized both reactions, H(2)S + F(2) and DMS + F(2), with high-level ab initio and generalized valence bond calculations. We found that recoupled pair bonding accounts for the structure and stability of the intermediates present in both reactions. Further, all sulfur products possess recoupled pair bonds with CH(2)S(F)CH(3) having an unusual recoupled pair bond dyad involving π bonding. In addition to explaining why DMS reacts readily with F(2) while H(2)S does not, we have studied the pathways for direct F(2) addition to both sulfide species ...Continue Reading

References

Jun 28, 2008·Accounts of Chemical Research·Arthur G Suits
Jun 9, 2009·The Journal of Physical Chemistry. a·David E Woon, Thom H Dunning
Jun 17, 2010·The Journal of Physical Chemistry. a·David E Woon, Thom H Dunning
Dec 21, 2010·The Journal of Physical Chemistry. a·Jeff LeidingThom H Dunning
Apr 16, 2011·The Journal of Physical Chemistry. a·Jeff LeidingThom H Dunning
Jan 14, 2012·The Journal of Physical Chemistry. a·Jeff LeidingThom H Dunning
Nov 16, 2012·Accounts of Chemical Research·Thom H DunningLina Chen

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Citations

Feb 26, 2016·The Journal of Physical Chemistry. a·Thom H DunningBeth A Lindquist
Jan 30, 2015·The Journal of Physical Chemistry. a·Tyler Y Takeshita, Thom H Dunning
Aug 9, 2016·The Journal of Physical Chemistry. a·Tyler Y Takeshita, Thom H Dunning
Jun 26, 2014·The Journal of Physical Chemistry. a·Beth A LindquistThom H Dunning
Apr 18, 2013·The Journal of Physical Chemistry. a·Lina ChenThom H Dunning
Jan 30, 2015·The Journal of Physical Chemistry. a·Tyler Y Takeshita, Thom H Dunning
Nov 16, 2012·Accounts of Chemical Research·Thom H DunningLina Chen
Dec 10, 2016·The Journal of Physical Chemistry. a·Tyler Y Takeshita, Thom H Dunning

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