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• W2051244744 abstract "Addition of excess HOSO2CF3 (HOTf) to CpRu(L)H (1) (L = dfepe = PR2CH2CH2PR2, R = C2F5) in CD2Cl2 under N2 produces a mixture of [CpRu(L)(H)2]+ (2a), [CpRu(L)(H2)]+ (2b), and CpRu(L)(OTf) (3) in a ratio of 1:5:2. Salts of the acid [HOEt2]+ are not strong enough to protonate 1. Complexes 2 slowly eliminate H2 to give 3; this reaction is slowed by adding excess HOTf. Of all such complexes [CpRu(PR2CH2CH2PR2)(H2)]+, R = alkyl and aryl, the dihydrogen complex 2b has the greatest acidity (similar to that of HOTf) and the related HD complex has the greatest JHD (29.1 Hz) because of the electron-withdrawing substituents R = C2F5. The reaction of 3 with 1 atm H2(g) proceeds much faster in the presence than in the absence of 1 equiv of HOTf to produce 1 and HOTf. This is a rare example of the production of a strong acid from H2(g) where the intermediate dihydrogen complex has been characterized. Reaction of Cp*Ru(L)Cl (4), Cp* = C5Me5, in dry CH2Cl2 at −78 °C with AgX salts under H2(g) (1 atm) gives mixtures of Cp*Ru(L)H (5) and [Cp*Ru(L)(H)2]+ (6), which have been identified by 1H NMR. 6 is deprotonated by traces of water or by PPh3 to give Cp*Ru(L)H (5). The addition of excess HOTf to mixtures of 5 and 6 under H2(g) produces 6. Complexes 3, 4, and 5 have been characterized by single-crystal X-ray diffraction. Complexes CpRu(L)Cl, 1, 4, and 5 have very positive redox potentials that indicate that the dfepe ligand has the electron-withdrawing power close to that of two carbonyl ligands." @default.
• W2051244744 created "2016-06-24" @default.
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• W2051244744 date "1998-11-13" @default.
• W2051244744 modified "2023-09-27" @default.
• W2051244744 title "Protonation and H₂ Heterolysis Reactions of Electrophilic (η⁵-C₅R₅)Ru(dfepe)(X) (R = H, Me; X = H, OTf) Complexes" @default.
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• W2051244744 doi "https://doi.org/10.1021/om980711u" @default.
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