Synthesis and Catalytic Properties of Dirhodium Paddlewheel Complexes with Tethered, Axially Coordinating Thioether Ligands.

Novel mixed-ligand rhodium(II) paddlewheel complexes incorporating tethered axial thioether ligands have been synthesized and characterized. The thioether moiety is essential for high yields and the suppression of byproducts in cyclopropanation reactions using an electron-deficient diazoacetate. Crystal structures, UV-vis analysis, and cyclic voltammetry experiments shed light on the catalytic performance of the complexes.

Crystal structure of bis-[1,3-bis-(di-phenyl-phosphan-yl)propane-κ(2) P,P']platinum(II) dichloride chloro-form penta-solvate.

In the title compound, [Pt{Ph2P(CH2)3PPh2}2]Cl2·5CHCl3, the Pt(II) cations, located on a centre of inversion, is coordinated by two chelating diphosphane ligands in a geometry which is close to square-planar. The chelate rings adopt a chair conformation. The Pt(II) cations are arranged in layers separated by Cl(-) anions as well as CHCl3 solvent mol-ecules.

The coordination chemistry of pentafluorophenylphosphino pincer ligands to platinum and palladium.

The synthesis of electron-poor PCP pincer ligands 1,3-((C6F5)2PO)2C6H4, 1,3-((C6F5)2PCH2)2C6H4, and 1-((C6F5)2PO)-3-(tBu2PCH2)C6H4, and their coordination chemistry to platinum and palladium is described. The most electron-poor ligand 1,3-((C6F5)2PO)2C6H4 (POCOPH) reacts with Group 10 metal chloride precursors to form a range of unusual cis, trans-dimers of the type κ(2)-P,P-[(POCOPH)MCl(L)]2 (M = Pt, Pd; L = Cl, Me), which undergo metallation to form [(POCOP)MCl] pincer complexes only under prolonged thermolysis. The formation of such cis,trans-dimers during pincer complex formation can be mitigated through the use of starting materials with more strongly binding ancillary ligands, improving the overall rate of ligand metallation.

Synthesis and characterization of the dinuclear polyhydrides [Os(2)H(7)(PPh(i)Pr(2))(4)](+) and [Os(2)H(6)(PPh(i)Pr(2))(4)].

The dinuclear osmium polyhydride [Os(2)H(7)(PPh(i)Pr(2))(4)][HC(SO(2)CF(3))(2)] (1) was synthesized by the protonation of [OsH(6)(PPh(i)Pr(2))(2)] with bis(trifluoromethylsulfonyl)methane. Treatment with amine bases was not able to deprotonate 1, but reaction with potassium hydride gave the corresponding neutral polyhydride [Os(2)H(6)(PPh(i)Pr(2))(4)] (2). Single crystal X-ray diffraction revealed that 1 and 2 both crystallize in the P2(1)/c space group and are classical polyhydrides containing similar Os(mu-H)(3)Os cores with Os-Os distances of 2.