| 19253994 |
Szymczak NK, Braden DA, Crossland JL, Turov Y, Zakharov LN, Tyler DR: Aqueous coordination chemistry of H2: why is coordinated H2 inert to substitution by water in trans-Ru (P2) 2 (H2) H+-type complexes (P2 = a chelating phosphine)?. Inorg Chem. 2009 Apr 6;48(7):2976-84.
The reactivity of a series of trans-Ru (P (2))(2) Cl (2) complexes with H (2) was explored. The complexes reacted with H (2) via a stepwise H (2) addition/heterolysis pathway to form the trans-[Ru (P (2))(2)(H (2)) H](+) dihydrogen complexes. Some of the resulting eta (2)-H (2) complexes were surprisingly inert to substitution by water, even at concentrations as high as 55 M; however, the identity of the bidentate phosphine ligand greatly influenced the lability of the coordinated eta (2)-H (2) ligand. With less electron-donating phosphine ligands, the H (2) ligand was susceptible to substitution by H (2) O, whereas with more electron-rich phosphine ligands, the H (2) ligand was inert to substitution by water. Density functional theory (DFT) calculations of the ligand substitution reactions showed that the Ru-H (2) and Ru-H (2) O complexes are very close in energy, and therefore slight changes in the donor properties of the bidentate phosphine ligand can inhibit or promote the substitution of H (2) O for H (2). |
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