Unusual rearrangement of modified PNP ligand based Ru complexes relevant to alcohol dehydrogenation catalysis

'Hangman-type' PNP pincer ligands and their associated Ru complexes undergo sp(2)-sp(3) C-C bond cleavage and subsequent C-C formation processes to form a new, one carbon unit longer backbone motif. DFT and mechanistic studies suggest a mechanism dependent upon arm pyridine coordination and ligand sterics.