The complex fac-[RuCl 3 (pdma)(NO)] [pdma = 1,2-phenylenebis(dimethylarsine)] reacts with silver(I) salts, AgX, at room temperature in acetonitrile to afford disubstituted derivatives cis-[RuClX 2 (pdma)(NO)] (X - = trifluoroacetate 1, p-toluenesulphonate 2 or nitrate 3). Reflux of fac-[RuCl 3 (pdma)(NO)] in 1 : 4 pyridine/methanol containing an excess of AgO 2 CCF 3 causes conversion into cis-[Ru(OMe)(pdma)(py) 2 (NO)][PF 6 ] 2 4 (py = pyridine). Reaction of fac-[RuCl 3 (pdma)(NO)] in refluxing 1 : 7 pyridine/acetonitrile containing 2 equivalents of AgO 2 CCF 3 affords cis-[RuCl(pdma)(py) 2 (NO)][PF 6 ] 2 (5). 5 is also prepared by reaction of 1 in refluxing pyridine/acetonitrile. The mixed-chelate salts trans-[RuCl(pdma)(L--L)(NO)][PF 6 ] n [n = 2, L--L = 2,2 -bipyridine 6, 1,10-phenanthroline 7, 4,4 -dimethyl-2,2 -bipyridine 8 or 1,2-bis(diphenylphosphino)ethane 9; n = 1, L--L = picolinate 10] are produced by reaction of fac-[RuCl 3 (pdma)(NO)] with an excess of L--L in refluxing methanol. The yields of the reactions to produce 5-10 vary according to the ligating ability of the incoming ligand(s). Single-crystal structures of fac-[RuCl 3 (pdma)(NO)], 2 Me 2 CO, 3 and 6 have been determined. 3 is the first ruthenium complex containing monodentate nitrato ligand(s) to be structurally characterized.