In methanol, solutions of iridium(III) tetrakis(p-sulfonatophenyl)porphyrin ([(TSPP)IrIII]) form a hydrogen ion dependent equilibrium distribution of iridium(III) methanol and methoxide spcies.  The acid dissociation constants of [(por)M(III)] (M = Rh, Ir) species in methanol are reported here and are compared to parallel studies in water.  The formation of an iridium hydride complex is accessible by reaction with dihydrogen and also by auto reduction of coordinated methanol.  The acid dissociation constant of [(TSPP)Ir?D(CD3OD)]4� is measured in methanol and is compared to the water analogue [(TMPS)Ir?D(D2O)]8? measured in water.  Reactions of iridium porphyrin hydride with alkenes occur to give both Markovnikov and anti-Markovnikov products.  Reactions of the iridium(I) complex with alkyhalides form iridium alkyl complexes.  Iridium porphyrin hydride in equilibrium with iridium(I) species in methanol are observed to catalyze the formation of  iridium methyl porphyrin complexes.  Bond dissociation free energies and energy differences were obtained from equilibrium thermodynamics from reactions measured experimentally and a comparison of M-X BDFEs where M = Rh, Ir and X = H, O, C is presented.

Methanol mediated reactivity and equilibrium thermodynamics of Ir-H and Ir<sup>III</sup> porphyrins

245th National Meeting (2013)

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Methanol mediated reactivity and equilibrium thermodynamics of Ir-H and IrIII porphyrins

Methanol mediated reactivity and equilibrium thermodynamics of Ir-H and Ir^III porphyrins