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Reactions of bis[diphenyl-3-(4-methoxyphenylsydnonyl)]phosphine palladium chloride and amines yielded trans-amminedichloropalladium complexes, which were characterized by spectroscopic techniques (compounds 5–9) and X-ray diffraction (compounds 5 and 7). Bond lengths of PC(10), P-(16) decrease more than that of P-(1) after the complex is formed, suggesting that the phenyl rings are able to contribute more electron density to phosphorus for binding with Pd(II) than the sydnone ring. The equilibrium constants and rate constants for the reaction between complex 4 and amines depend not only on the basicity but also on the steric size of amines used.

Dissolution of [CpRu(PPh 3 )(SC 4 H 8 ) 2 ]CF 3 SO 3 in thietane/CH 2 Cl 2 with stirring yields the title compound [CpRu(PPh 3 )(SC 3 H 6 ) 2 ]CF 3 SO 3 ( I ). The single crystal X-ray structure shows a disparity in the puckering of the two thietanes. One thietane ligand is near-planar, with torsion angles of ±1.5(5)° for CSCC and ±1.8(4)° for CCCS; the second thietane ligand of I has torsion angles of ±21.0(4)° for CSCC and ±25.0(3)° for CCCS. Compound I contains both the largest and the smallest torsion angles for any complex reported. Theoretical calculations were carried out for both thietane and for I using the gamess and gaussian 98 packages.

The isolation and characterization of the trimethylenesulfide-coordinated complex, [CpRu(PPh3)2(SC3H6)]CF3SO3, is reported. The structure of [CpRu(PPh3)2(SC3H6)]CF3SO3 was determined by X-ray diffraction techniques: monoclinic space group I2/a, a=23.864(10), b=14.233(3), c=24.385(7) A, β=97.10(3)°, Z=8, R=0.046, Rw=0.065. The Ru is attached to two triphenylphosphine ligands, a cyclopentadienyl and the trimethylenesulfide. The Ru-S distance is 2.3459(20) A.

The isolation and characterization of two mercaptan complexes of the general formula [CpRu(PPh3)2(RSH)]BF4, where R=benzyl and phenethyl, were undertaken to model the substrate/catalyst interaction of the hydrode-sulfurization (HDS) process. The IR data show a shift in the SH stretching frequency upon coordination. The structure of the [CpRu(PPh3)2(C6H5CH2CH2SH)]BF4 complex was determined by X-ray diffraction techniques: monoclinic space group P21/n, a=15.317(4), b=13.924(9), c=21.815(7) A, β=95.20(2)°, Z=4, R=0.057, Rw=0.073. The Ru is attached to two triphenylphosphine ligands, a cyclopentadienyl and the phenethylmercaptan. The Ru-S distance is 2.369(2) A and the S-H distance is 1.18 A.