Organometallics
Organometallics
4 years ago

Evidence for Reversible Cyclometalation in Alkane Dehydrogenation and C–O Bond Cleavage at Iridium Bis(phosphine) Complexes

Evidence for Reversible Cyclometalation in Alkane Dehydrogenation and C–O Bond Cleavage at Iridium Bis(phosphine) Complexes
Nathan D. Schley, Scott M. Chapp
Methyl tert-butyl ether is found to undergo C–O bond cleavage in the formation of an iridium(III) methallyl at a cationic bis(phosphine) iridium complex. An exploration of this transformation has revealed a cyclometalated complex which was previously postulated to form reversibly in the first example of alkane dehydrogenation by a homogeneous transition-metal complex. The competence of this cyclometalated species in alkane dehydrogenation is demonstrated in a stoichiometric example, giving an isolable olefin dihydride. Detection and assignment of this elusive species confirms a previous hypothesis that reversible intramolecular phosphine cyclometalation can precede intermolecular alkane dehydrogenation.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00676

DOI: 10.1021/acs.organomet.7b00676

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