Reactions of 2-azidopyridine and 1-pyridinio ylides with transition-metal complexes

The reactions of 2-azidopyridine (L 1) and 1-pyridinio ylides C 5H 5N +-N -R [R = O 2SC 6H 4Me-p (L 2) or OCC 6H 4Me-p (L 3)] with metal(II) halogeno-complexes give derivatives of formula [MnL 1 2Cl 2], [FeL 1 3Cl 2], [CoL 1Cl 2], [CuL 1Cl 2], [ZnL 1 2Cl 2], [(NiL 1Cl 2) n], [NiL 1 2Br 2], [(NiL 2Cl 2) n], [NiL 2 2Br 2], [PdL 1 2Cl 2], [PdL 2 2Cl 2], [PdL 3 2Cl 2], [Ru(PPh 3) 2L 1 2X 2], and [Ru(SbPh 3) 2L 1 2Cl 2] (X = Cl or Br). The complexes [M(CO) 5L 1] (M = W or Cr) have been obtained from [M(CO) 5(thf)] (thf = tetrahydrofuran) and tetrazolopyridine. In these complexes L 1 is present in its tetrazole form. From [Pt(SMe 2) 2Cl 2] and L 1, [Pt(SMe 2)L 1Cl 2] has been isolated, while L 3 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(PPh 3) 2L 1 2Cl 2] reacts with carbon monoxide to give [Ru(PPh 3) 2(CO)L 1Cl 2]. 2-Azido-5-nitropyridine (RN 3) reacts in its azide form with the hydride [Pt(PEt 3) 2H(Cl)] to give the amido-complex [Pt(PEt 3) 2(NHR)Cl] and with [Pt(PPh 3) 2(C 2H 4)] to give a complex of composition [Pt(PPh 3) 2(N 3)(N 2R)]. The spectroscopic properties of the new complexes are reported and their structures discussed.