Reactions of 2-azidopyridine and 1-pyridinio ylides with transition-metal complexes
Abstract
The reactions of 2-azidopyridine (L1) and 1-pyridinio ylides C5H5N–NR [R = O2SC6H4Me-p(L2) or OCC6H4Me-p(L3)] with metal(II) halogeno-complexes give derivatives of formula [MnL12Cl2], [FeL13Cl2], [CoL1Cl2], [CuL1Cl2], [ZnL12Cl2], [(NiL1Cl2)n], [NiL12Br2], [(NiL2Cl2)n], [NiL22Br2], [PdL12Cl2], [PdL22Cl2], [PdL32Cl2], [Ru(PPh3)2-L12X2], and [Ru(SbPh3)2L12Cl2](X = Cl or Br). The complexes [M(CO)5L1](M = W or Cr) have been obtained from [M(CO)5(thf)](thf = tetrahydrofuran) and tetrazolopyridine. In these complexes L1 is present in its tetrazole form. From [Pt(SMe2)2Cl2] and L1, [Pt(SMe2)L1Cl2] has been isolated, while L3 gives a derivative in which the aryl group is metallated in the position ortho to the carbonyl group and the ylide is bidentate. The complex [Ru(PPh3)2L12Cl2] reacts with carbon monoxide to give [Ru(PPh3)2(CO)L1Cl2]. 2-Azido-5-nitropyridine (RN3) reacts in its azide form with the hydride [Pt(PEt3)2H(Cl)] to give the amido-complex [Pt(PEt3)2(NHR)Cl] and with [Pt(PPh3)2(C2H4)] to give a complex of composition [Pt(PPh3)2(N3)(N2R)]. The spectroscopic properties of the new complexes are reported and their structures discussed.