A comprehensive understanding of carbon–carbon bond formation by alkyne migratory insertion into manganacycles

Migratory insertion (MI) is one of the most important processes underpinning the transition metal-catalysed formation of C–C and C–X bonds. In this work, a comprehensive model of MI is presented, based on the direct observation of the states involved in the coupling of alkynes with cyclometallated ligands, augmented with insight from computational chemistry. Time-resolved spectroscopy demonstrates that photolysis of complexes [Mn(C^N)(CO)(4)] (C^N = cyclometalated ligand) results in ultra-fast dissociation of a CO ligand. Performing the experiment in a toluene solution of an alkyne results in the initial formation of a solvent complex fac-[Mn(C^N)(toluene)(CO)(3)]. Solvent substitution gives an η(2)-alkyne complex fac-[Mn(C^N)(η(2)-R(1)C(2)R(2))(CO)(3)] which undergoes MI of the unsaturated ligand into the Mn–C bond. These data allowed for the dependence of second order rate constants for solvent substitution and first order rate constants for C–C bond formation to be determined. A systematic investigation into the influence of the alkyne and C^N ligand on this process is reported. The experimental data enabled the development of a computational model for the MI reaction which demonstrated that a synergic interaction between the metal and the nascent C–C bond controls both the rate and regiochemical outcome of the reaction. The time-resolved spectroscopic method enabled the observation of a multi-step reaction occurring over 8 orders of magnitude in time, including the formation of solvent complexes, ligand substitution and two sequential C–C bond formation steps.