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DOI: 10.1039/A702846F (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 3185-3188

The synthesis and characterization of technetium and rhenium hydrazinopyrimidine chelate complexes[hair space]

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Melissa Hirsch-Kuchma, Terrence Nicholson, Alan Davison, William M. Davis and Alun G. Jones

Abstract

Organohydrazide chelate complexes of rhenium and technetium, which are defined as complexes containing a metal–nitrogen–nitrogen linkage, have been synthesized using 2-hydrazino-4-(trifluoromethyl)pyrimidine. The complexes all contain a chelating organohydrazide that forms a five-membered ring with the metal center. The chelate ring forms a delocalized π system and contributes to the unique electronic characteristics of these d4, octahedral complexes, which all have 1H NMR spectra characteristic of diamagnetic complexes. An X-ray structural analysis of TcIII(NNC4H2N2CF3 )(PPh3)2Cl2 1 was obtained. Complex 1, C41H32Cl2F3N4P 2Tc, crystallizes in the triclinic space group P[1 with combining macron] with a = 11.9193(3), b = 12.7026(3), c = 14.1335(3) Å, α = 109.9320(10), β = 94.1250(10), γ = 105.0490(10)°, U = 1912.14(8) Å3, Z = 2 and R = 0.0737 based on 3528 unique reflections. The complex ReIII(NNC4H2N2CF3 )(PPh3)2Cl2 2 was prepared and characterized. Both 1 and 2 contain a uninegative, chelating diazenido ligand. An X-ray structural analysis of ReIII(NNC4H2N2CF3 )(HNNC4H2N2CF3)(PPh 3)Cl2 3 was obtained. Complex 3, C28H20Cl2F6N8PRe, crystallizes in the monoclinic space group P21/c with a = 10.1292(2), b = 14.92310(10), c = 20.6924(4) Å, β = 92.4560(10)°, U = 3124.97(9) Å3, Z = 4 and R = 0.0807 based on 4472 unique reflections. Complex 3 contains a monodentate, uninegative diazenido ligand and a chelating, α-nitrogen protonated, neutral diazene ligand.

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