Thioether, Dinitrogen, and Olefin Complexes of (PNP)Rh: Kinetics and Thermodynamics of Exchange and Oxidative Addition Reactions

Abstract

A variety of (PNP)Rh−L complexes (where L = organic sulfide or sulfoxide, dinitrogen, or tert-butylethylene) have been synthesized by trapping transient (PNP)Rh (1) in situ. Equilibrium studies established the relative affinity of the (PNP)Rh fragment (1) for various L in the following order (of decreasing affinity): Ph2SO > SBun2 > SPhMe > dibenzothiophene > SPh2 > benzothiophene > SPri2 > thiophene ≈ SButMe > SBus2 ≈ H2CCHCMe3 ≫ SBut2. Dinitrogen reacted with 1 to yield a mixture of terminal and bridging N2 complexes and was found to bind more strongly than SPri2. Reaction of (PNP)Rh(SPri2) (10) with PhHal led to the corresponding oxidative addition products (PNP)Rh(Ph)(Hal) (Hal = Cl, 18a; Hal = Br, 18b; Hal = I, 18c). The relative rates of oxidative addition of PhHal to 10 were found to be in the order PhI > PhBr > PhCl. Kinetic studies of the reaction of 10 with PhBr were consistent with the reaction proceeding via reversible dissociation of SPri2, followed by irreversible addition of PhBr. Evidence...