Abstract
The reactions of trithiazyltrichloride in tetrahydrofuran with RuCl 2(PPh 3) 3, RuBr 2(PPh 3) 3, RuCl 3(AsPh 3) 2·MeOH and RuBr 3(AsPh 3) 2·MeOH give crystalline thionitrosyl complexes Ru(NS)Cl 3(PPh 3) 2, Ru(NS)Br 2Cl(PPh 3) 2, Ru(NS)Cl 3(AsPh 3) 2, Ru(NS)Br 2Cl(AsPh 3) 2 and two novel mixed ligand thionitrosyls Ru(NS)Cl 3(PPh 3)AsPh 3) and Ru(NS)Cl 3(AsPh 3)(SbPh 3). On irradiation with UV light in air these compounds form a pentacoordinated species Ru(NS)X 3L and the corresponding oxides of triphenylphosphine, arsine or stibine. When Ru(NS)X 3L is treated excess L′, mixed thionitrosyl complexes are obtained. On treating these with NOX( X = Cl, Br, Br 3) mixed nitrosyl complexes are obtained, presumably through a pentacoordinated species as an intermediate in the presence of excess ligand L′ (L = PPh 3, AsPh 3; L′ = PPh 3, AsPh 3, SbPh 3, Py). The reactions of dinitrogen trioxide in presence of an excess of the corresponding ligand give nitrosyl nitrato complexes of the general form Ru(NO)(NO 3)X 2L 2.
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