Reaction of Pt3(CO)3(P-tert-Bu2Ph)3 and hydrogen chloride. The x-ray structure of Pt2Cl2(CO)2(P-tert-Bu2Ph)2

Hexacarbonyldiplatinum(I). Synthesis, Spectroscopy, and Density Functional Calculation of the First Homoleptic, Dinuclear Platinum(I) Carbonyl Cation, [{Pt(CO)3}2]2+, Formed in Concentrated Sulfuric Acid

“…A significant decrease in the R factor (to 7.96%) resulted, while the Pt−C and Pt−Pt bond distances were invariant within the normal precision (±0.01 Å), giving the mean lengths of the Pt−Pt and Pt−C bonds of 2.718 and 1.960 Å, respectively. The Pt−Pt distance of 2.718 Å for 1 is longer than that found for [{PtCl 2 (CO)} 2 ] 2- (2.584 Å), [{PtCl(CO)(P- t -Bu 2 Ph)} 2 ] (2.628 Å), and [{Pt(C 6 F 5 )(CO)(PPh 3 )} 2 ] (2.599 Å), but shorter than that found for Pt metal (2.774 Å) . The mean Pt−C distance of 1.960 Å is longer than that found for cis -Pt(CO) 2 (SO 3 F) 2 (1.854 Å);7b this is consistent with the observation that the CO ligands are more weakly bound to Pt(I) in 1 than to Pt(II) in 2 since evacuation of 1 results in the formation of 2 through loss of CO. From the mean lengths of Pt−Pt, Pt−C, and Pt−C‘, the cis C−Pt−Pt bond angle is calculated to be approximately 85.6°, indicating displacement of the equatorial CO ligands toward the neighboring Pt atom as predicted by the geometric optimization using B3LYP.…”

“…This structure is related to [{PtCl 2 (CO)} 2 ] 2- which contains two slightly distorted T-shaped PtCl 2 (CO) groups with a dihedral angle of 60° between the two planes and both the CO's on each group are cis to the Pt−Pt bond (2.584 Å) . Other related, crystallographically characterized dinuclear platinum carbonyls include [{PtCl(CO)(P- t -Bu 2 Ph)} 2 ] and [{Pt(C 6 F 5 )(CO)(PPh 3 )} 2 ], which have the following dihedral angles, with the Pt−Pt distance (Å) given in parentheses, 70.1° (2.628), and 78.6° (2.599), respectively. Preliminary reports have also appeared for [{PtCl(CO)(PPh 3 )} 2 ] 31 and, in all cases, the carbonyls are cis and the two phosphines are trans to the Pt−Pt bond.…”

Oxidative addition of iodo-acetonitrile and of elemental halogens to [Pt3(µ-CO)3(PCy3)3]

“…The 1 J(Pt-P) and 1 J(Pt-C) values of 2617 and 1945 Hz, respectively, are similar to corresponding values in isostructural complexes. 14,24 Complexes with other halides show the expected decrease in values of 1 J(Pt-P) in accordance with the increased electronegativity of the halide and the decreased s-electron density of the Pt-P bond. The observed 2 J(Pt-P) value (198 Hz) of 4a is significantly smaller than that of the above referred complexes, or in 4b (250 Hz) and in 4c (344 Hz), but is close to the value of 219 Hz found in the Pt(I) dimer [Pt 2 I 2 (CO) 2 (P t Bu 2 Ph) 2 ].…”

“…The planes defined by the ligands about the two Pt centres are approximately perpendicular with a dihedral angle of 76.5 • which is larger than the observed value of 66.5 • in the related complex with a polyaromatic phosphine, 24 and the value of 70.1 • observed in the dimer with P t Bu 2 Ph. 14 This arrangement of the two planes renders the complex chiral. The iodide and the CO group around the Pt2 centre are disordered, in the sense that the iodide ligand occupies the position of the CO ligand in 20% of the molecules which are present in the crystal.…”

Cationic Hydridotriplatinum Complex with Bridging Germylene Ligands

“…Complexes 2a , b are thermally stable and have been purified by recrystallization in air. Farrar reported that [{Pt(P t Bu 2 Ph)} 3 (μ-CO) 3 ], having a triangular structure, reacted with HCl to afford mono- and dinuclear Pt complexes with Cl ligands . A similar reaction of HCl with complexes 1a , b , however, yielded products whose structures were not determined. …”