American Chemical Society
ja202439g_si_001.pdf (1.48 MB)

Mechanism of N/O Bond Scission of N2O by an Unsaturated Rhodium Transient

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journal contribution
posted on 2011-08-17, 00:00 authored by José G. Andino, Kenneth G. Caulton
The mechanism of formation of triplet (PNP)RhO and (PNP)Rh(N2) (PNP = N(SiMe2CH2PtBu2)2) from reaction of two molecules of (PNP)Rh with N2O has been studied by DFT, evaluating mechanisms which (1) involve free N2, and (2) which effect N/O bond scission in linearly coordinated (PNP)RhNNO. This work shows the variety of modes of binding N2O to this reducing, unsaturated metal fragment and also evaluates why a mechanism avoiding free N2 is preferred. Comparisons are made to isoelectronic CO2 in its reaction with (PNP)Rh.