Reactivity of Rhodium(I) Iminophosphine Carbonyl Complexes with Methyl Iodide

A series of Rh(I) iodocarbonyl complexes, [Rh(CO)I(PNAr)] (1a−g), has been prepared by the reactions
of [Rh(CO)2I]2 with iminophosphine ligands, Ph2PC6H4-2-CHNAr (PNAr; Ar = C6H5 (a), 2,6-Me2C6H3
(b), 2,6-iPr2C6H3 (c), 2-EtC6H4 (d), 2-MeOC6H4 (e), 4-MeOC6H4 (f), 3,5-(CF3)2C6H3 (g)). For 13CO-labeled 1b, a relatively small 2JCP coupling (12 Hz) showed the CO ligand to be cis to the P-donor atom
of the iminophosphine. Complexes 1a−g react with methyl iodide to give Rh(III) methyl or acetyl products.
For complexes 1a,d,f,g the reactions result in equilibria between the methyl complexes [Rh(CO)(PNAr)I2Me] (2) and acetyl complexes [Rh(PNAr)(COMe)I2] (3), whereas the reactions of 1b,c,e gave only the
acetyl products [Rh(COMe)I2(PNAr)] (3b,c,e). Migratory CO insertion is promoted for systems in which
the N-aryl group of the iminophosphine is bulky or contains an o-methoxy substituent. An X-ray structure
of 3e reveals an interaction between the Rh center and the o-methoxy group (Rh−O = 2.54 Å). Second-order rate constants for MeI oxidative addition to 1a−g vary considerably, depending on the steric and
electronic properties of the iminophosphine N-aryl substituents. The most reactive complex is 1e, and a
mechanism is proposed in which the o-methoxy group interacts with the Rh center to promote both
oxidative addition and CO insertion.