Synthesis and crystal structure of bis(1,4,7-triazacyclononane-NN′)platinum(II) dibromide dehydrate and its facile oxidation by oxygen: characterisation of bis(1,4,7-triazacyclononane-NN′N″)platinum(IV) tetraperchtorate

Abstract
1,4,7-Triazacyclononane (L) reacts with [PtCl4]2– in aqueous solution to form a variety of complexes containing the potentially tridentate amine as a uni- or bi-dentate ligand. The complex [PtII(L)2]Br2·2H2O containing two bidentate ligands was oxidised by molecular oxygen in aqueous solution to form the octahedral cation [PtIV(L)2]4+. 1H N.m.r. spectra indicated that the two cyclic amines were co-ordinated via six N-donor atoms. The X-ray crystal structure of [PtII(L)2]Br2·2H2O was determined. The complex crystallises in space group P2/n, with a= 8.990(2), b= 7.987(2), c= 14.424(4)Å, β= 93.34(2)°, and Z= 2. 1 419 Independent reflections with I > 2.5σ(I) gave R= 0.0335. The geometry of the complex cation is essentially square planar with one unco-ordinated nitrogen atom per bound amine ligand.

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