The preparation and properties of M(Bu,dtc),X, (M = Pd, Pt and X = Br, I) are reported. From the platinum complexes two isomers were isolated. The crystal structure of the cis-isomer of Pt(Bu,dtc),I, is determined by a three-dimensiona1 X-ray analysis. The orthorhombic cell, space group Fddd, with a = 33.37(3), b = 34.16(3), c = 20.19(2) A and V = 2301q40) A3 contains 32 formula units. Atomic parameters were refined to a conventional R value of 0.073 for 1417 independent nqn-zero reflections. The platinum atom is distorted octahedrally coordinated by two iodine and four sulfur atoms with average distances of Pt -I = 2.66 and Pt -S = 2.35 A. The intra-and one of the intermolecular 1-1 distances (resp. 3.79 and 3.37 A) are short compared with an 1-1 Van der Waals contact. ESCA spectra show the other isomer to be a Pt(IV) complex too. NMR data suggest a rrans-structure for this isomer.With Bu,tds these complexes yield M(Bu,dtc),X (M = Pt, Pd and X = Br, I) of which some properties are given.
Experimental sectionAs starting materials for the preparation of the compounds K,PdCI, and K,PtCI, (Drijthout) were used. M(Bu,dtc), was synthesized following the general procedure described by Thorn and Ludwig5, using commercial CS, (Brocades) and Bu,NH(BDH). Bu,tds was commercially available (FIuka).Analyses. The C, H and N analyses were carried out in the micro analytical department of this university. Pd and P t were analysed by atomic absorption spectrophotometry using aqua regia solutions of the metals as standards.Spectra. Infrared spectra in the 400@625 cm-' region were measured on a Perkin-Elmer 257 infrared spectrophotometer in KBr pellets. The spectra in the 700-200 cm-' region were measured on a Hitachi -EPI -L instrument in CsI disks.
Magnetic susceptibility was measured with a standard Gouy type balance.Electrical conductivity measurements were performed with a Metrohm Konduktoskop E 365 and a Philips PR 9510/00 conductivity cell at 25°C. The nitrobenzene was purified by freezing and vacuum destillation.