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).