Increasing the Lability of Polarised Phosphorus–Phosphorus Bonds

Diphosphanes with polarised P–P bonds react readily with Lewis acids like borane, gallium trichloride, or with elemental selenium, to give products arising from electrophilic attack at the more basic phosphorus atom and consecutive bond cleavage. Spectroscopic studies proved that the initial reaction with borane proceeds under preservation of the P–P bond to give a transient phosphane–borane which rearranged below ambient temperature. The results suggest that Lewis acid coordination decisively enhances the weakening of the polarised P–P bond. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

[1]  N. N. Greenwood,et al.  Infrared spectra and structure of phosphine and substituted phosphine complexes of gallium trihalides , 1968 .

[2]  H. Schmidbaur,et al.  Phosphane-borane chemistry. Open-chain and cyclic phosphane-boranes based on tetramethyldiphosphane , 1989 .

[3]  D. Gudat,et al.  Phosphorus-carbon bond formation catalysed by electrophilic N-heterocyclic phosphines. , 2006, Chemical communications.

[4]  C. A. Russell,et al.  The surprising and stereoselective formation of P2C10 cages by the reduction of Cp*PCl2. , 2006, Chemical communications.

[5]  Gudat,et al.  Stability and electrophilicity of phosphorus analogues of arduengo carbenes--an experimental and computational study , 2000, Chemistry.

[6]  H. Schmidbaur,et al.  Dichlorogallane (HGaCl(2))(2): its molecular structure and synthetic potential. , 2002, Inorganic chemistry.

[7]  J. Grobe,et al.  Untersuchungen zum reaktiven verhalten von (CF3)2PPH2 und (CF3)2AsPH2 , 1973 .

[8]  M. Ziegler,et al.  Tellurierung und Selenierung von Tetra‐tert‐butyldiphosphan , 1989 .

[9]  A. Carty.  Coordination complexes of gallium(III) and indium(III) halides. II. Far-infrared spectra of gallium(III) halide complexes with triarylphosphines , 1967 .

[10]  R. McDonald,et al.  Phosphine ligand exchange at a phosphine lewis acceptor: the first structural characterization of homoleptic phosphinophosphonium salts. , 2001, Journal of the American Chemical Society.

[11]  M. Nieger,et al.  Metal-assisted, reversible phosphinyl phosphination of the carbon-nitrogen triple bond in a nitrile. , 2007, Angewandte Chemie.

[12]  G. Sheldrick.  Phase annealing in SHELX-90: direct methods for larger structures , 1990 .

[13]  J. Brunel,et al.  Phosphane–boranes: synthesis, characterization and synthetic applications , 1998 .

[14]  M. Nieger,et al.  P-hydrogen-substituted 1,3,2-diazaphospholenes: molecular hydrides. , 2006, Journal of the American Chemical Society.

[15]  H. Flack,et al.  On enantiomorph‐polarity estimation , 1983 .

[16]  J. Nash,et al.  Phosphorus–phosphorus nuclear spin coupling in tetraorganobiphosphines and some of their derivatives , 1980 .

[17]  M. Nieger,et al.  Synthese und Struktur von Bis[bis(diisopropylamino)phosphino]chalkogeniden , 1991 .

[18]  A. B. Burg,et al.  The Hybrid Diphosphine (CH3)2PP(CF3)2 , 1962 .

[19]  M. Nieger,et al.  Diphosphanes with polarized and highly reactive P-P bonds. , 2004, Angewandte Chemie.

[20]  R. McDonald,et al.  Phosphine coordination complexes of the diphenylphosphenium cation: a versatile synthetic methodology for P-P bond formation. , 2003, Journal of the American Chemical Society.

[21]  M. Nieger,et al.  Umpolung of P−H Bonds , 2000 .

[22]  J. Nelson,et al.  Transition Metal-Catalyzed Formation of Phosphorus−Boron Bonds: A New Route to Phosphinoborane Rings, Chains, and Macromolecules , 2000 .

[23]  J. Holz,et al.  Borane Complexes of Trivalent Organophosphorus Compounds. Versatile Precursors for the Synthesis of Chiral Phosphine Ligands for Asymmetric Catalysis , 1998 .

[24]  M. A. Malik,et al.  Metal complexes of selenophosphinates from reactions with (R2PSe)2Se: [M(R2PSe2)n] (M = ZnII, CdII, PbII, InIII, GaIII, CuI, BiIII, NiII; R = iPr, Ph) and [MoV2O2Se2(Se2PiPr2)2] , 2006 .

[25]  Michael J. Taylor,et al.  Raman spectra and vibrational assignments of the molecular adducts PhnPH3−n GaCl3 (n=1-3) , 1984 .

[26]  M. Nieger,et al.  2-Chloro-1,3,2-diazaphospholenes – A Crystal Structural Study , 2007 .