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Gold(I) complexes bearing monophosphole ligands were synthesized, and their electronic and steric properties were compared to those of their triphenylphosphine-based counterparts. Cationic phosphole-based gold(I) complexes are active and selective in enyne cycloisomerization and in olefin cyclopropanation, with a good correlation between the ligand σ-donor ability and the catalytic activity. For the most efficient ligand, 1-phenyl-2,3,4,5-tetramethylphosphole (TMP), a highly active, selective, and stable cationic [Au(TMP)(CH 3 CN)]SbF 6 complex was isolated.

The first dibenzophospholyl(diphenylphosphino)methane-borane hybrid ligand has been prepared from a Pd-catalyzed reaction of (chloromethyl)diphenylphosphine-borane with the dibenzophospholyl anion. This borane precursor is readily synthesized using a promising new reaction of diphenylphosphine-borane with dichloromethane, under phase transfer catalysis (PTC) conditions. The dibenzophospholyl(diphenylphosphino)methane-borane acts as a chelating P-(η 2 -BH 3 ) ligand to afford an air-stable Rh(I) complex. The X-ray crystal structure of this complex shows complexation of both benzophospholyl and borane moieties.

This review provides an overview of phosphole-based ligand families (monophospholes, multidentate hybrid phosphole ligands, diphosphole and 2,2′-biphosphole-based ligands) and their potential in metal- and organo-catalyzed reactions (asymmetric reactions included).

A convenient one-pot procedure for the preparation of 1-(diisopropylamino)phospholes has been developed. These phospholes have been used in a multistep procedure for synthesizing two new 2,2Ј-biphosphole disulfide compounds. The structures and stereochemistry of these compounds have been studied by X-ray diffraction analysis and by molecular

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