Reactivity of [ReOX3(AsPh3)2] (X = Cl, Br) complexes towards gaseous nitric oxide.: Crystal, molecular and electronic structure of [ReBr3(NO)(OAsPh3)2], [ReCl3(NO)(AsPh3)2][ReCl4(AsPh3)2], [ReCl4(OAsPh3)2] and [ReBr3(NO)(AsPh3)2]

The reactions of the complexes [ReOX3(AsPh3)(2)] (X = Cl, Br) with gaseous nitric oxide and the reactions of the compounds [NBu4](2)[ReX5(NO)] (X = Cl, Br) with an excess of triphenylarsine have been examined. [ReOBr3(AsPh3)(2)] reacts with nitric oxide to give mer,cis-[ReBr3(NO)(OAsPh3)(2)] (1), whereas the reaction of the chlorine oxocomplex with NO leads to three products: [ReCl3(NO)(OAsPh3)(2)] (2), mer, trans -[ReCl3(NO)(AsPh3)(2)][ReCl4(AsPh3)(2)] (3) and cis-[ReCl4(OAsPh3)(2)] (4). The compounds [NBu4](2)[ReX5(NO)] (X = Cl, Br) react with an excess of AsPh3 to give 3 and mer, trans-[ReBr3(NO)(AsPh3)(2)] (5), respectively. The complexes obtained in these reactions have been characterised by IR, UV-Vis and magnetical measurements. Crystal and molecular structures have been determined for complexes 1 and 3-5. EPR spectra have been recorded for compounds 1 and 5. (C) 2002 Elsevier Science Ltd. All rights reserved.