CATIONIC AND NEUTRAL CHLORIDE COMPLEXES OF PALLADIUM(2) WITH NONAQUEOUS SOLVENT DONORS ACETONITRILE DIMETHYL SULFOXIDE AND A SERIES OF AMIDES . MIXED SULFUR AND OXYGEN COORDINATION SITES IN A DIMETHYL SULFOXIDE COMPLEX

Nitrosyl tetrafluoroborate dissolved in acetonitrile reacts with metallic palladium to form [Pd(CH3CN)4](BF4)2, which functions as a convenient precursor to other cationic palladium(II) complexes. Cationic Pd(II) complexes of the type [PdL4]X2 along with neutral [PdL2Cl2] complexes, where L is CH3CN, DMSO, DMF, DMA, NMF, or NMA and X is the noncoordinating perchlorate or tetrafluoroborate, have been prepared and partially characterized. All complexes were found to be diamagnetic with the metal ion contributing a small paramagnetism. Infrared spectra (4000-270 cm-1) were recorded and assignments for the main absorption bands were used to determine the ligand donor sites and to comment on the relative acceptor ability of palladium(II). The complex Pd(DMSO)42+ has the novel feature of containing both sulfur- and oxygen-bonded dimethyl sulfoxide. The ir spectra are most consistent with two sulfur and two oxygen coordination sites in a cis configuration. The solid sulfur-bonded complex trans-Pd(DMSO)2Cl2 is found to convert to the cis complex in acetonitrile solution. © 1969, American Chemical Society. All rights reserved.