The complexes: RhCl(P–N)(THP), where P–N is P,N-chelated o-diphenylphosphino-N,N-dimethylaniline and THP is tris(hydroxymethyl)phosphine, and RhCl[(O)P–N][THP(O)] containing O-bonded phosphine oxides
作者:Fabio Lorenzini、Brian O. Patrick、Brian R. James
DOI:10.1016/j.ica.2007.11.017
日期:2008.7
Abstract The complex RhCl(P–N)(THP) (1) is synthesized under argon from RhCl(cod)(THP) and P–N, and is structurally characterized; P–N = P,N-chelated o-diphenylphosphino-N,N-dimethylaniline, THP = tris(hydroxymethyl)phosphine, and cod = 1,5-cyclo-octadiene. The corresponding synthesis in air yields RhCl[(O)P–N][THP(O)] (2), containing O-bonded phosphineoxide ligands.
Serendipitous syntheses of Rh(H)2Cl(PRPh2)3 complexes, and their crystal structures, where R=Me, Cy (cyclohexyl)
作者:Fabio Lorenzini、Brian O. Patrick、Brian R. James
DOI:10.1016/j.ica.2007.10.044
日期:2008.5
Reactions of RhCl(cod)(THP) (cod = 1,5-cyclooctadiene; THP = P(CH2OH)(3)) with PMePh2 or PCyPh2 (Cy = cyclohexyl) in acetone/MeOH solution under H-2 surprisingly form the complexes cis,mer-Rh(H)Cl-2(PRPh2)(3) (R = Me or Cy); both complexes are characterized by crystallography (the first structures in which the hydride ligands of such dihydrido-chloro-trisphosphine complexes have been located), and by detailed H-1 and P-31 NMR spectroscopy. The key role of the THP in the observed chemistry is discussed. (C) 2007 Elsevier B.V. All rights reserved.
Formation of a Phosphine−phosphinite Ligand in RhCl(PRR‘<sub>2</sub>)[<i>P</i>,<i>P</i>-R‘(R)POCH<sub>2</sub>P(CH<sub>2</sub>OH)<sub>2</sub>] and R‘H from <i>cis</i>-RhCl(PRR‘<sub>2</sub>)<sub>2</sub>[P(CH<sub>2</sub>OH)<sub>3</sub>] via P−C Bond Cleavage
作者:Fabio Lorenzini、Brian O. Patrick、Brian R. James
DOI:10.1021/ic7012182
日期:2007.10.1
Reaction of RhCl(1,5-cod)(THP), where THP = P(CH2OH)(3), with several PRR'(2) phosphines (R = or not equal R') generates, concomitantly with R'H, the derivatives RhCl(PRR'(2))[PP-R'(R)POCH2P(CH2OH)(2)] in two isomeric forms. The hydrogen of the hydrocarbon co-product derives from, a THP hydroxyl group which becomes an 'alkoxy' group at the residual PRR' moiety, this resulting in the P,P-chelated R'(R)POCH2P(CH2OH)2 ligand. One of the isomers of the PPh3 system, cis-RhCl (PPh3)[P, P-P(Ph)(2)OCH2P(CH2OH)(2)], was structurally characterized (cis refers to the disposition of the P atoms with Ph substituents).