Cyclodimerization of selected fluoroalkenes by low-valent metal complexes affords fluorometallacyclopentanes, as first demonstrated by Stone and Wilkinson.[1,2] Although a mechanism for hydrocarbon analogs was proposed in a computational paper,[3] that with fluoroalkenes has not yet been reported. Using DFT we now show that conversion of L2Ni(C2F4)2 to the L2Ni(C4F8) metallacycle is accompanied by a significant opening of the L-Ni-L angle perpendicular to the metallacycle plane (cf. 145°). This observation accounts for the lack of reactivity of chelating nitrogen ligand Ni TFE complexes with additional TFE[4] and has additional consequences for wide bite angle bis(phosphines) that will be presented. Finally, the reactivity of several ring-functionalized nickelacycles will be detailed and compared to their perfluorinated analogs.

Fluorometallacycles built for two: Understanding formation mechanism and reactivity

ACS Spring 2022

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