The reaction of [Rh(NO)(NCMe),(PPh,),] [BF,], with Na[RNNNR] (R = p-tolyl) in tetrahydrofuran yields [Rh(NO)( PPh,),( RNNNR)] [BF,], X-ray diffraction studies on which have revealed a trigonal-bipyramidal structure with a linear nitrosyl [ Rh-N-0 177.5( 6)"] and chelating triazenide ligand in the equatorial positions.We have recently described ' the synthesis, electrochemistry, and structural and spectroscopic characterisation of a range of triazenido-bridged binuclear complexes, derived from [ {Rh-(CO),(p-RNNNR)),] (1; R = p-tolyl) and containing [Rh2JL' (Z = 2, 3, or 4) cores. In order to extend and diversify this range, we have attempted to substitute C O in (1) and its derivatives by the isoelectronic [NO] + group, thereby altering the overall charge of the complex without changing the oxidation state of the central Rh, core. The direct reaction of the binuclear carbonyl complexes, for example, [Rh,(CO),-(PPh,)l(p-RNNNR)2], with nitrosonium salts invariably results in one-electron oxidation. We have therefore sought alternative synthetic routes, and now report o n the reaction of [Rh(NO)(NCMe)'( PPh,),][BF,], * (Di-p-tolyltria~~nid~~)nitrosylbis(triphenylphosphine)rhodium tet rafluoro bora te d ichloromet hane ( 1 / 1 ).