Metal–Ligand Proton Tautomerism, Electron Transfer, and C(sp(3))–H Activation by a 4-Pyridinyl-Pincer Iridium Hydride Complex

[Image: see text] The para-N-pyridyl-based PCP pincer proligand 3,5-bis(di-tert-butylphosphinomethyl)-2,6-dimethylpyridine (pN-(tBu)PCP-H) was synthesized and metalated to give the iridium complex (pN-(tBu)PCP)IrHCl (2-H). In marked contrast with its phenyl-based congeners, e.g., ((tBu)PCP)IrHCl and derivatives, 2-H is highly air-sensitive and reacts with oxidants such as ferrocenium, trityl cation, and benzoquinone. These oxidations ultimately lead to intramolecular activation of a phosphino-t-butyl C(sp(3))–H bond and cyclometalation. Considering the greater electronegativity of N than C, 2-H is expected to be less easily oxidized than simple PCP derivatives; cyclic voltammetry and DFT calculations support this expectation. However, 2-H is calculated to undergo metal–ligand-proton tautomerism (MLPT) to give an N-protonated complex that can be described with resonance forms representing a zwitterionic complex (with a negative charge on Ir) and a p-N-pyridylidene (a remote N-heterocyclic carbene) Ir(I) complex. One-electron oxidation of this tautomer is calculated to be dramatically more favorable than direct oxidation of 2-H (ΔΔG° = −31.3 kcal/mol). The resulting Ir(II) oxidation product is easily deprotonated to give metalloradical 2(•) which is observed by NMR spectroscopy. 2(•) can be further oxidized to give cationic Ir(III) complex, 2(+), which can oxidatively add a phosphino-t-butyl C–H bond and undergo deprotonation to give the observed cyclometalated product. DFT calculations indicate that less sterically hindered analogues of 2(+) would preferentially undergo intermolecular addition of C(sp(3))–H bonds, for example, of n-alkanes. The resulting iridium alkyl complexes could undergo facile β-H elimination to afford olefin, thereby completing a catalytic cycle for alkane dehydrogenation driven by one-electron oxidation and deprotonation, enabled by MLPT.