A new route to N(1)-5R-tetrazole complexes via azidation to nitriles coordinated to Pt(II) and Pt(IV)

New tetrazolate complexes trans-[PtCl2(RCN4)(2)](2), trans-[PtCl4(RCN4)(2)](2) with Ph3PCH2Ph+ and (CH3)(2)NH2+ counterions have been obtained by azidation of nitriles coordinated to Pt(II) and Pt(IV) {trans-[PtCl2(RCN)(2)] and trans-[PtCl4(RCN)(2)] (R = Et, Ph)} and characterized. The composition and the molecular structure of the complexes obtained were established by the CHN elemental analyses, H-1 and C-13 NMR spectroscopy, IR spectroscopy, mass spectrometry, and X-ray diffraction. The coordination of nitriles to Pt(II) and Pt(IV) is shown significantly activate the azidation: the reaction proceeds with a higher rate and at relatively low temperature compared with the classical 1,3-dipolar addition of azides to nitriles. (C) 2011 Elsevier B.V. All rights reserved.