2020
DOI: 10.1021/jacs.0c10458
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Metal/Ligand Proton Tautomerism Facilitates Dinuclear H2Reductive Elimination

Abstract: Using the doubly protic bis-pyrazole-pyridine ligand (N­(NNH)2), we have synthesized an octahedral IrIII–H [HIr­(κ3-N­(NNH)­(NN–))­(CO)­( t BuPy)]+ ([1-MH]+) from an IrI starting material. This hydride was generated by adding sufficient electron density to the metal center such that it became the thermodynamically preferred site of protonation. It was observed via UV–vis spectroscopy that [1-MH]+ establishes a [ t BuPy] dependent equilibrium with a ligand protonated square-planar IrI [Ir­(N­(NNH)2)­(CO)]+ ([2-… Show more

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Cited by 19 publications
(23 citation statements)
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“…53 Furthermore, in related studies of MLPT, Rauchfuss, Bullock, and our group have previously demonstrated that the MLPT equilibrium can be perturbed towards the ligand-protonated side by addition of an exogenous hydrogen bonding acceptor such as BF 4 − or CF 3 SO 3 − that can engage in favorable hydrogen bonding interactions with the acidic proton on the ligand backbone. 9,17,18 A similar hydrogen bonding stabilization of the imidazolyl protons is proposed here that disrupts the MLPT equilibrium of [ LH Ir–Cl] with [H– L Ir–Cl] ( Scheme 1, C ) upon addition of excess Cl anions, precluding the formation of latter.…”
Section: Resultssupporting
confidence: 54%
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“…53 Furthermore, in related studies of MLPT, Rauchfuss, Bullock, and our group have previously demonstrated that the MLPT equilibrium can be perturbed towards the ligand-protonated side by addition of an exogenous hydrogen bonding acceptor such as BF 4 − or CF 3 SO 3 − that can engage in favorable hydrogen bonding interactions with the acidic proton on the ligand backbone. 9,17,18 A similar hydrogen bonding stabilization of the imidazolyl protons is proposed here that disrupts the MLPT equilibrium of [ LH Ir–Cl] with [H– L Ir–Cl] ( Scheme 1, C ) upon addition of excess Cl anions, precluding the formation of latter.…”
Section: Resultssupporting
confidence: 54%
“…To consider how [H-L Ir-Cl] might originate from [ LH Ir][Cl] in solution, one can either propose that proton-transfer from the imidazole to the Ir occurs rst and is followed by Cl À coordination, or that Cl À coordination is followed by ligand to metal proton-transfer. Based on literature precedent wherein addition of electron density to the metal center (thereby increasing its basicity) has been shown to trigger proton-transfer from the ligand to the metal, 9 it is expected that proton-transfer from the…”
Section: Resultsmentioning
confidence: 99%
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