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- W1999063462 abstract "Absolute rate constants for hydrogen atom abstraction by benzyl radical from Os3(μ-H)2(CO)9PPh3 (1), Os3(μ-H)(H)(CO)10PPh3 (2), Os3(μ-H)(CO9)(μ3-η2-C9H6N) (3), Os3(μ-H)(CO9)(μ-η2-C9H6N)(PPh3) (4), and Os3(μ-H)(CO10)(μ-η2-C9H6N) (5) were determined in benzene by competition of the abstraction reaction with the self-termination of benzyl radical. Thus, experimental values of kabs/kt1/2 were combined with rate constants for self-termination of benzyl radical in benzene from the expression ln(2kt/M-1 s-1 = 27.23 − 2952.4/RT), RT in cal/mol, to give absolute rate constants for abstraction, kabs: for Os3(μ-H)2(CO)9PPh3 (1) in benzene, log(kabs/M-1 s-1) = (9.40 ± 0.30) − (8.11 ± 0.47)/θ; for Os3(μ-H)(H)(CO)10PPh3 (2) log(kabs/M-1 s-1) = (8.08 ± 0.33) − (4.32 ± 0.1)/θ; for Os3(μ-H)(CO)9(μ3-η2-C9H6N) (3) log(kabs/M-1 s-1) = (10.1 ± 2) − (10.5 ± 3)/θ; and for Os3(μ-H)(CO9)(μ-η2-C9H6N)(PPh3) (5) log(kabs/M-1 s-1) = (7.0 ± 0.27) − (4.25 ± 0.41)/θ, θ = 2.303RT kcal/mol. The terminal hydride on the Os3 cluster 2 is ab..." @default.
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- W1999063462 date "2003-12-31" @default.
- W1999063462 modified "2023-10-18" @default.
- W1999063462 title "Comparison of Hydrogen Atom Abstraction Rates of Terminal and Bridging Hydrides in Triosmium Clusters: Absolute Abstraction Rate Constants for Benzyl Radical" @default.
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- W1999063462 doi "https://doi.org/10.1021/om0342255" @default.
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