[Cp*Rh] hydride complexes are invoked as intermediates in certain catalytic cycles, but few of these species have been successfully prepared and isolated, contributing to a relative shortage information on the properties such species. Here, synthesis, isolation, characterization two hydrides reported; supported by chelating diphosphine ligands bis(diphenylphosphino)methane (dppm) 4,5-bis(diphen...

Treatment of bis(diphenylphosphino)amine (dppa) with (dimethylsulfide)gold(I) chloride in the molar ratio 1:2 leads to the dinuclear complex (dppa)Au2Cl2 in 95% yield. The compound was crystallized from diethyl ether/dimethylformamide as the 1:1 solvate with dmf, the crystal struc­ ture of which has been determined. The complex features an intramolecular Au—Au contact [3.121(1) A] and an interm...

Stepwise oxidation of 1,8-bis(diphenylphosphino)naphthalene and a series of (oligo)methylene-linked diphosphines with XeF2 followed by fluoride abstraction yields a family of compounds featuring phosphine, phosphonium and phosphorane moieties in close proximity. The bisphosphonium ions [(C10H6)(Ph2PF)2]2+ (5) and [CH2(Ph2PF)2]2+ (9a) exhibit remarkable Lewis acidity arising from the proximity o...

{Rh(xantphos)}-based phosphido dimers form by P-C activation of xantphos (4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) in the presence of amine-boranes. These dimers are active dehydrocoupling catalysts, forming polymeric [H2 BNMeH]n from H3 B⋅NMeH2 and dimeric [H2 BNMe2 ]2 from H3 B⋅NMe2 H at low catalyst loadings (0.1 mol %). Mechanistic investigations support a dimeric active species, su...

A methylzirconocene cation (with a [B(C(6)F(5))(4)](-) counterion) transfers a methyl cation equivalent to diphenylphosphino-alkynes to generate (η(2)-alkyne)ZrCp(2) complexes bearing the [RC≡CPPh(2)Me](+) ligand. Two examples of the PMe(3) ligand stabilized [(Me(3)P)Cp(2)Zr(η(2)-RC≡CPPh(2)Me)(+)][B(C(6)F(5))(4)(-)] salts were characterized by X-ray diffraction.