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- W1985930225 abstract "Os(H)3ClL2 (L = PiPr3) forms a 1:1 adduct with L‘ = PEt3, NH3, MeCN, acetone, methanol, and THF. The case L‘ = PEt3 permits the clearest identification of adduct structure as pentagonal bipyramidal. For NH3 and MeCN, the respective kinetics of L‘ loss are measured as ΔH⧧ = 20.7(3) and 17.6(3) kcal/mol and ΔS⧧ = 16(1) and 14.7(9) cal/(mol K). For acetone, methanol, and THF, the following respective ΔH° and ΔS° values for L‘ binding are measured: ΔH° = −10.4(1), −6.66(8), and −5.8(2) kcal/mol; ΔS° = −41.8(5), −25.5(3), and −33(1) cal/(mol K). Decoalesced 1H NMR spectra are reported for several of these Os(H)3ClL2L‘ species, and they show a variety of examples of quantum exchange coupling among the hydride ligands. The values of Jex are higher when L‘ is a more weakly-binding ligand. The quantum exchange coupling constants of Os(H)3XL2 (X = Cl, Br, I, OCH2CF3, OCH(CF3)2) in CD2Cl2, in toluene, and in methylcyclohexane show an unprecedented decrease of J with increasing temperature, which is attributed to we..." @default.
- W1985930225 created "2016-06-24" @default.
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- W1985930225 date "1997-10-01" @default.
- W1985930225 modified "2023-09-26" @default.
- W1985930225 title "Quantum Exchange Coupling: A Hypersensitive Indicator of Weak Interactions" @default.
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- W1985930225 doi "https://doi.org/10.1021/ja970603j" @default.
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