Experimental and computational study of alkane dehydrogenation catalyzed by a carbazolide-based rhodium PNP pincer complex.

ABSTRACT: A rhodium complex based on the bis-phosphine carbazolide pincer ligand was investigated in the context of alkane dehydrogenation and in comparison with its iridium analogue. (carb-PNP)RhH2 was found to catalyze cyclooctane/t-butylethylene (COA/TBE) transfer dehydrogenation with a turnover frequency up to 10 min-1 and turnover numbers up to 340, in marked contrast with the inactive Ir analogue. TONs were limited by catalyst decomposition. Through a combination of mechanistic, experimental and computational (DFT) studies the difference between the Rh and Ir analogues was found to be attributable to the much greater accessibility of the 14-electron (carb-PNP)M(i) fragment in the case of Rh. In contrast, Ir is more strongly biased toward the M(iii) oxidation state. Thus (carb-PNP)RhH2 but not (carb-PNP)IrH2 can be dehydrogenated by sacrificial hydrogen acceptors, particularly TBE. The rate-limiting segment of the (carb-PNP)Rh-catalyzed COA/TBE transfer dehydrogenation cycle is found to be the dehydrogenation of COA. Within this segment, the rate-determining step is calculated to be (carb-PNP)Rh(cyclooctyl)(H) undergoing formation of a ?-H agostic intermediate, while the reverse step (loss of a ?-H agostic interaction) is rate-limiting for hydrogenation of the acceptors TBE and ethylene. Such a step has not previously been proposed as rate-limiting in the context of alkane dehydrogenation, nor, to our knowledge, has the reverse step been proposed as rate-limiting for olefin hydrogenation.

SUBMITTER: Bezier D 

PROVIDER: S-EPMC5477040 | biostudies-literature | 2016 Apr

REPOSITORIES: biostudies-literature