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.