摘要:
NBD ligand (NBD = 2,5-norbornadiene, bicyclo[2,2,1]hepta-2,5-diene) was easily displaced from [Rh(quin)(NBD)] (quin = 2-quinaldinate, C9H6NCOO-) by PR3 phosphine ligands [R = (4-X-C6H4)3, X = CH3O, CH3, F, Cl] to produce the disubstituted [Rh(quin)(PR3)2] complexes. These reactions occur through a penta-coordinate intermediate, [Rh(quin)(NBD)(PR3)], whose stability in solution suggests an associative mechanism when PR3 = P(4-CH3OC6H4)3, P(4-CH3C6H4)3 and an interchange mechanism when PR3 = P(4-F-C6H4)3, P(4-ClC6H4)3. Reactions of [Rh(quin)(NBD)] with diphosphine ligands, dppe [1,2-bis(diphenylphosphino)ethane] or dppm [bis(diphenylphosphino) methane], gave rise to the [Rh(quin)(P-P)] complexes (P-P = dppe, dppm) which had been previously prepared from [Rh(quin)(CO)2]. A binuclear intermediate [{Rh(quin)(NBD)}2(mu-P-P)] has been isolated in the above reactions. Comparison between the behaviour of [Rh(quin)(CO)2] and [Rh(quin)(NBD)] towards PR3 or P-P ligands is established. Conclusions related to the influence of leaving or substituent ligands to produce complexes of the type [Rh(quin)(P)2] [(P)2 = 2PR3, P-P] were deduced.