C–Cl Oxidative addition and C–C reductive elimination reactions in the context of the rhodium-promoted direct arylation

A cycle of stoichiometric elemental reactions defining the direct arylation promoted by a redox-pair Rh(I)–Rh(III) is reported. Starting from the rhodium(I)-aryl complex RhPh{κ3-P,O,P-[xant(PiPr2)2]} (xant(PiPr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene), the reactions include C–Cl oxidative addition of organic chlorides, halide abstraction from the resulting six-coordinate rhodium(III) derivatives, C–C reductive coupling between the initial aryl ligand and the added organic group, oxidative addition of a C–H bond of a new arene, and deprotonation of the generated hydride-rhodium(III)-aryl species to form a new rhodium(I)-aryl derivative. In this context, the kinetics of the oxidative additions of 2-chloropyridine, chlorobenzene, benzyl chloride, and dichloromethane to RhPh{κ3-P,O,P-[xant(PiPr2)2]} and the C–C reductive eliminations of biphenyl and benzylbenzene from [RhPh2{κ3-P,O,P-[xant(PiPr2)2]}]BF4 and [RhPh(CH2Ph){κ3-P,O,P-[xant(PiPr2)2]}]BF4, respectively, have been studied. The oxidative additions generally involve the cis addition of the C–Cl bond of the organic chloride to the rhodium(I) complex, being kinetically controlled by the C–Cl bond dissociation energy; the weakest C–Cl bond is faster added. The C–C reductive elimination is kinetically governed by the dissociation energy of the formed bond. The C(sp3)–C(sp2) coupling to give benzylbenzene is faster than the C(sp2)–C(sp2) bond formation to afford biphenyl. In spite of that a most demanding orientation requirement is needed for the C(sp3)–C(sp2) coupling than for the C(sp2)–C(sp2) bond formation, the energetic effort for the pregeneration of the C(sp3)–C(sp2) bond is lower. As a result, the weakest C–C bond is formed faster.Financial support from the MICIN/AEI/10.13039/501100011033 (PID2020-115286GB-I00 and RED2018-102387-T), Gobierno de Aragón (E06_20R and LMP23_21), FEDER, and the European Social Fund is acknowledged. L.A.d.l.H. thanks the MECD for her FPU contract (FPU17/04813, “ESF investing in your future”).Peer reviewe