Facile oxidation of a bound nitrosyl group to a nitrato ligand: Preparation and structures of cis-dibromonitrosylbis(dicyclohexyl-phosphine)rhodium, [RhBr 2(NO){P(C 6H 11) 2H} 2] and trans-dibromonitratobis (dicyclohexylphosphine)rhodium, [RhBr 2(NO 3){P(C 6H 11) 2H} 2

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The synthesis and structure of the tetragonal pyramidal complex [RhBr 2(NO) {P(C 6H 11) 2H} 2] are reported. This complex has a cis-disposition of basal ligands with an apical nitrosyl group inclined towards the bromide ligands. [RhBr 2(NO){P(C 6H 11) 2H} 2] readily and irreversibly takes up atmospheric dioxygen to form the nitrato complex [RhBr 2(NO 3){P(C 6H 11) 2H} 2], whose structure is also described. In this complex the bromide and phosphine ligands are trans- and cis-disposed, respectively.