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Mapping The Reaction Coordinate For The Oxidative Addition Of Molecular Hydrogen To A Metal Center

By Saikat Dutta

Abstract

The binding of molecular hydrogen to a metal center leads to the elongation of the H−H bond and subsequently to its cleavage along the reaction coordinate for the oxidative addition of H2. There has been considerable interest in the study of the activation of dihydrogen and map out the reaction coordinate for the homolysis of H2 on a metal center. A large number of H2 complexes reported to date possess H−H distances ranging from 0.8 to 1.0 Å. A relatively fewer examples of elongated dihydrogen complexes wherein the H−H distances fall in the range of 1.0 to 1.5 Å, are known. Study of the elongated dihydrogen complexes is of great significance because of its relevance in important catalytic processes such as hydrogenation, hydrogenolysis, and hydroformylation. Objectives The objectives of this work are as follows: (a) Synthesis and characterization of elongated dihydrogen complexes with chelating phosphine coligands by varying the electron donor ability. (b) Trap the various intermediate states in the process of oxidative addition of H2 to a metal center. (c) Map the reaction coordinate for the oxidative addition for the oxidative addition of H2 to a metal center. Results We have synthesized and characterized two new elongated dihydrogen complexes cis-[Ir(H)(η2-S2CH)(η2-H2)(PR3)2][BF4] (PR3 = PCy3, PPh3) wherein hydrogen atom undergoes site exchange between the H2 and the hydride sites. The dynamics of the exchange was studied using NMR spectroscopy. In addition, a series of ruthenium dihydrogen complexes of the type trans-[Ru(Cl)(η2-H2)(PP)][BF4] (PP = 1,2- Synopsis bis(diarylphosphino)ethane) has been synthesized and characterized wherein the aryl group is a benzyl moiety with a substituent (p-fluoro, H, m-methyl, p-methyl, p-isopropyl); in this series of complexes, a small increment in the electron donor ability (decrease in Hammett substituent constants) of the chelating phosphine ligand resulted in an elongation of the H−H bond by a small, yet significant amount. We also synthesized a series of 16-electron dicationic dihydrogen complexes bearing elongated dihydrogen ligand. In addition, we prepared a series of dihydrogen complexes of the type [RuCp/Cp*(PP)(η2-H2)][OTf] (PP = 1,2-bis(diarylphosphino)ethane, 1,2-bis(diarylphosphino)methane, 1,2-bis(dialkylphosphino)methane) bearing elongated H2 ligand (dHH = 1.0 to 1.17 Å); in this series of complexes as well, we found that the H−H bond distances increased as the donor ability of the chelating phosphines increased in small increments, along the reaction coordinate for the oxidative addition of H2 to a metal center. This investigation therefore, has established a very nice correlation between the H−H bond lengths and the Hammett substitutent constants (donor properties) resulting in the construction of dihydrogen complexes along the reaction coordinate for the oxidative addition of H2 to a metal center

Topics: Hydrolysis Reactions, Hydride Complexes, Chelating Phosphine Ligand, H-H Bond Elongation, Iridium Dihydrogen Complexes, Ruthenium Dihydrogen Complexes, Elongated Dihydrogen Complexes, Electron Dictationic Dihydrogen Complexes, Transition Metal Dihydrogen Complexes, Molecular Hydrogen - Binding, Metal Center, Elongated H2 Complexes, Iridium, Phosphine Coligands, Elongated Dihydrogen Ligands, Dihydrogen/Hydride Complex, Physical Chemistry
Year: 2008
OAI identifier: oai:etd.ncsi.iisc.ernet.in:2005/754
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