Ligand Effects on Reactivity of Cobalt Acyl Complexes

Hydrogenolysis reactions of cobalt acyl complexes, [Co(CO) 3 (L)(COR)] (L = phosphine, R = Me, n Pr) have been monitored using in situ IR spectroscopy at moderate temperatures (<75 °C) and pressures (<25 bar). The reactions provide a model for the product-formation step in phosphine-modified, cobalt-catalyzed hydroformylation. The reaction kinetics are dependent on L, with the fastest rate being observed for the complex containing n -pentyl-9-phosphabicyclo[4.2.1]nonane ( a 5 -PhobPC 5 ). The observed dependence of rate on H 2 and CO pressure is consistent with a mechanism involving initial CO dissociation, followed by reaction of [Co(CO) 2 (L)(COR)] with H 2 . Isotopic exchange experiments, monitored by IR spectroscopy, demonstrate that both terminal and acetyl carbonyls of [Co(CO) 3 (L)(COR)] exchange with free 13 CO. Kinetic data are also reported for reactions of [Co(CO) 3 (L)(COR)] with triphenyltinhydride. A zero-order dependence on [Ph 3 SnH] (at large excess) and positive values of Δ S ‡ demonstrate rate-determining CO dissociation. For a series of less bulky, symmetrical phosphines, the rates follow the sequence PEt 3 < PMe 2 Ph ∼ PEtPh 2 < PPh 3 < P(4-ClC 6 H 4 ) 3, in accord with their electron-donating strength. Higher rates are found for more bulky phosphines, and the fastest rate is again found for L = a 5 -PhobPC 5 . Calculations using density functional theory indicate that the CO dissociation energy for [Co(CO) 3 (L)(COMe)] is influenced by the stereoelectronic properties of L, with steric bulk having a substantial effect. X-ray crystal structures are reported for [Co(CO) 3 (PEtPh 2 )(COMe)], [Co(CO) 3 ( s -PhobPC 5 )] 2, and [Co(CO) 3 ( a 5 -PhobPC 5 )] 2 .