B–H Bond Cleavage via Metal–Ligand Cooperation by Dearomatized Ruthenium Pincer Complexes

Abstract

Organic derivatives of boronic acid are widely used reagents useful in various synthetic applications. A fundamental understanding and the exploration of new reaction pathways of boronic reagents with organometallic systems hold promise for useful advancement in chemical catalysis. Herein we present the reactions of simple boranes with dearomatized ruthenium pincer complexes based on PNP (2,6-bis­(di-<i>tert</i>-butylphosphinomethyl)­pyridine) or PNN (2-(di-<i>tert</i>-butylphosphinomethyl)-6-(diethylaminomethyl)­pyridine) ligands. NMR studies revealed dehydrogenative addition of the borane B–H bond across the metal center and the ligand. Remarkably, new complexes were observed, which contain the boryl moiety at the benzylic carbon of the pincer ligand arm. X-ray crystal structures of new dearomatized boryl pincer complexes were obtained, and DFT calculations revealed mechanistic details of the adduct formation process through a dehydrogenative pathway. In addition, catalytic aryl–boron coupling reactions were explored. The new boryl pincer systems may possibly be useful in future postmodification techniques for ruthenium pincer complexes, as well as in catalytic B–B and B–C coupling reactions