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- W2495507935 abstract "Octaethylporphyrin rhodium II dimer, [(OEP)Rh]2, reacts with H2 and CO to produce an equilibrium distribution of hydride and formyl complexes (Equations 1-3).1,2 Thermodynamic and kinetic measurements for this system have [(OEP)Rh]2 + H2 ⇄ 2 (OEP)Rh-H (1) 2 (OEP)Rh-H + 2 CO ⇄ 2 (OEP)Rh-CHO (2) [(OEP)Rh]2 + 2 CO + H2 ⇄ 2 (OEP)Rh-CHO (3) provided estimates for the effective Rh-Rh, Rh-H and Rh-C bond energies: (OEP)Rh-Rh(OEP) (~16.0 kcal mol-1), (OEP)Rh-H (~62 kcal mol-1), (OEP)Rh-CHO (~58 kcal mol-1). 3,4 Approximate bond energy-thermochemical relationships for organometallic reactions (Table I) have subsequently been used in anticipating new types of reactivity for the (OEP)Rh system and in guiding our efforts to modify reactivity through ligand steric and electronic effects. Reductive coupling of CO to form dimetal 1,2-ethanedione complexes5 and hydrocarbon reactivity6 are examples of anticipated [(OEP)Rh]2 reactivity. Ligand modifications suggested by thermodynamic and mechanistic considerations have been effectively used in achieving selectivity for CO reductive coupling7,8 and methane activation.9 This article summarizes the thermodynamic measurements and reasoning used in organizing and interpreting reactivity studies of rhodium macrocycles relevant to CO reduction." @default.
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- W2495507935 date "1990-06-25" @default.
- W2495507935 modified "2023-09-27" @default.
- W2495507935 title "Thermodynamic Studies of the Hydrogenation and Reductive Coupling of Carbon Monoxide by Rhodium(II) Porphyrins" @default.
- W2495507935 doi "https://doi.org/10.1021/bk-1990-0428.ch010" @default.
- W2495507935 hasPublicationYear "1990" @default.
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