Thermal and Photolytic Reactions of Nitrosyl-Carbonyl Complexes of Rhodium and Iridium with Triphenylphosphine

Mitsuru Kubota, Michael K. Chan, David C. Boyd, Kent R. Mann

Research output: Contribution to journalArticlepeer-review

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Abstract

The photolysis of [Rh(NO)(CO)(PPh3)2] in the presence of PPh3in dichloromethane results in the expulsion of NO rather than CO and the formation of trans-[Rh(CO)Cl(PPh3)2]. The thermal reaction and photoreaction of [Ir(NO)(CO)Cl(PPh3)2]BF4(1) with PPh3lead to dissociation of NO and the formation of the Ir(II) radical [Ir(CO)Cl(PPh3)3]BF4(2). The demonstration of the homolytic cleavage of the Ir-NO bond of 1 provides support for the proposal that the photodissociation of NO instead of CO in the compounds [M(NO)(CO)(PPh3)2] (where M is Rh or Ir) proceeds from a charge-transfer state that has a bent M-N-0 bond.

Original languageEnglish (US)
Pages (from-to)3261-3264
Number of pages4
JournalInorganic Chemistry
Volume26
Issue number20
DOIs
StatePublished - Oct 1 1987

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