Synthesis and structure of a series of thiophosphinato-bridged platinum complexes. Crystal and molecular structure of bis-.mu.-(diethylphosphido sulfide)bis(triphenyl phosphite)diplatinum

Platinum(0)-platinum(0) dimers. Bonding relationships in a d10-d10 system

“…The orbitals of the Fe(CO)4 fragment are well known.203 '25 Let us focus our attention on the highest occupied one, 17, which is of bi symmetry, and the lowest unoccupied one, 18, of ai symmetry. 17 and 18 interact respectively with xa* and xd as shown in Figure 5. The antibonding combination between ai (18) and xd is stabilized by mixing with and consequently lies below xd*, which is destabilized through the interaction with bi ( 17).…”

Solvent-Driven P–S vs P–C Bond Formation from a Diplatinum(III) Complex and Sulfur-Based Anions

“…These kinds of complexes containing a neutral tertiary thiophosphano ligand, R 2 P–SR′, with an “M–P–S–M’” skeleton (M, M′ = any transition metal) has not previously been characterized structurally by X-ray diffraction (CSD version 5.38, updated May 2017). Three entries were found in the CSD for the “Pt–P–S–Pt” skeleton if the two metal centers are linked by a bridging R 2 P–S – thiophosphinate anion . − The sulfur atom in 2 – 4 can be regarded as forming single covalent bonds with a phosphorus atom and carbon atom and donating formally two electrons to the platinum atom, resulting in a pyramidal coordination in agreement with the existence of a lone pair. Nevertheless, the Pt(2)–S distances, as well as the P–S distances, in 2 – 4 (see Table S2) are not very different from those observed in the reported thiophosphinate complexes in which the sulfur atom establishes two chemical bonds. − The pyramidal geometry of the sulfur bridging atom bonded to three different substituents renders such an atom chiral.…”

“…Three entries were found in the CSD for the "Pt-P-S-Pt" skeleton if the two metal centres are linked by a bridging R 2 P-Sthiophosphinate anion. [47][48][49] The sulfur atom in 2-4 can be regarded as forming single covalent bonds with a phosphorous and a carbon atoms and donating formally two electrons to the platinum atom, resulting in a pyramidal coordination in agreement with the existence of a lone pair.…”

“…Nevertheless, the Pt(2)-S distances, as well as the P-S ones, in 2-4 (see Table S2) are not very different from those observed in the reported thiophosphinate complexes in which the sulfur atom establishes two chemical bonds. [47][48][49] The pyramidal geometry of the sulfur bridging atom bonded to three different substituents renders such atom chiral. Table S1 (See Supporting Information).…”

Synthesis and Characterization of η3-Allyl Palladium(II) Complexes with Tetraalkyldiphosphine Disulfides, R2P(S)P(S)R2 (R=Me, Et, nPr, nBu, Ph)

“…This certainly occurs when a number of square-planar platinum complexes react with Et 4 P 2 S 2 . [15] The two complexes PdX 2 .tmps where X=Cl or Br were assigned a structure involving a five-membered ring as in Figure 3. [16] Since studies of the reactions of η 3 -allylic palladium(II) complexes containing chelating ligands with unsaturated hydrocarbons suggest that such complexes may be useful for a variety of organic synthesis and as model systems for catalytic reactions, [17] we considered it worthwhile to synthesize some η 3 -allyl complexes of palladium(II) with tetraalkyldiphosphine disulfide, R 2 P(S)P(S)R 2 (R=Me, Et, n Pr, n Bu, Ph) ligands as potentially bidentate chelating agents.…”