Formation of a phosphine-phosphinite ligand in RhCl(PRR'2)[P,P-R'(R)POCH2P(CH2OH)2] and R'H from cis-RhCl(PRR'2)2[P(CH2OH)3] via P-C bond cleavage.
Reaction of RhCl(1,5-cod)(THP), where THP = P(CH(2)OH)(3), with several PRR'2 phosphines (R = or not equal R') generates, concomitantly with R'H, the derivatives RhCl(PRR'(2))[P,P-R'(R)POCH(2)P(CH(2)OH)(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)POCH(2)P(CH(2)OH)(2) ligand. One of the isomers of the PPh(3) system, cis-RhCl(PPh(3))[P,P-P(Ph)(2)OCH(2)P(CH(2)OH)(2)], was structurally characterized (cis refers to the disposition of the P atoms with Ph substituents).
Lorenzini
Fabio
F
Department of Chemistry, The University of British Columbia, Vancouver, British Columbia, Canada, V6T 1Z1.
Patrick
Brian O
BO
James
Brian R
BR
D002384:Catalysis; D002621:Chemistry / Q000379:methods*; D018360:Crystallography, X-Ray / Q000379:methods; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008670:Metals / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D010720:Phosphines / Q000737:chemistry*; D010758:Phosphorus; D021241:Spectrometry, Mass, Electrospray Ionization; D013696:Temperature
D008024:Ligands; D008670:Metals; D010720:Phosphines; D010758:Phosphorus