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Through DFT calculations, the equilibrium between Rh–alkyne and Rh–vinylidene species of PXNXP pincer ligated Rh cationic complexes is shown to be tuned by the P–Rh–P bite angle, which in turn is dictated by the nature of the X moiety of the pincer ligand.

DFT calculations bring insight to internal alkyne-to-vinylidene transformations at rhodium PNP- and PONOP-pincer complexes