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Ruthenium, Diazide, ZINDO/1 CalculationsThe reaction of [Ru(tpy)(PPh3)(Cl)2] (tpy = 2,2':6',2"-terpyridine) with sodium azide in acetone/water afforded [Ru(tpy)(PPh3)(N3)2]. The new Ru-diazide complex was fully char acterized by elemental analysis, IR, Raman, and multinuclear NMR spectroscopy. The struc tures, energies and vibrational frequencies of the ruthenium diazide isomers, cis-and trans-[Ru(tpy)(PMe3)(N3)2] (Me=CH0, were calculated at the semi-empirical ZINDO/1 level of theory.

The structures of the compounds [Rh(bpy)2(py)(Cl)](C104)2 (2 (C10 4 )2) and [Rh(phen)2(py)-(C1)](C104)2 (7 -(C10 4 )2) were determined by single-crystal X-ray diffraction. Both complexes show a six-coordinate rhodium atom with two bpy or phen ligands in the cis configuration. The Rh-Cl distances are 2.334(3) and 2.323(2) A, respectively. The bond angles N-Rh-Cl formed with the axially-positioned nitrogen atom are 174.4(2) and 173.8(2)°. The oxidation of aquo complexes, prepared from the corresponding rhodium chloride complexes, by two equivalents of Ce(IV) in 60% HCIO4 solution yields the corresponding mono-oxo products. All complexes have been identified and characterized by elemental analyses, IR, and H NMR data.