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• W2090985831 abstract "Abstract Titration curves were measured for three molybdocene dimers, [Cp 2 Mo(μ-OH)] 2 [OTs] 2 ( 4 ), [ Cp 2 ′ Mo(μ-OH)] 2 [OTs] 2 ( 4′ ; Cp′ = C 5 H 4 CH 3 ), and ansa -[C 2 Me 4 Cp 2 Mo(μ-OH)] 2 [OTs] 2 ( 4 a ), and for two monomeric molybdocene complexes, Cp 2 MoO ( 6 ) and Cp 2 MoCl 2 ( 1 ). The titration curves for 4 , 6 , and 1 were identical and showed three equivalence points each. The titration curve for 4′ was also similar in appearance but the equivalence points were shifted higher by ∼0.3, as expected for the more electron-rich Mo center in this molecule. The titration curve for the ansa -[C 2 Me 4 Cp 2 Mo(μ-OH)] 2 [OTs] 2 complex showed only two equivalence points. Two of the equivalence points observed in the titration of 4 , 6 , and 1 were previously reported in potentiometric measurements of aqueous solutions of Cp 2 MoCl 2 and were attributed to the Cp 2 Mo(OH 2 ) 2+ species (p K a  = 5.5 ± 0.1 and 8.3 ± 0.2). The third equivalence point (p K a  = 2.2 ± 0.2) is assigned to protonation/deprotonation of the [Cp 2 Mo(μ-OH)] 2 [OTs] 2 /[Cp 2 Mo(μ-OH 2 )(μ-OH)MoCp 2 ] 3+ dimer. A new equilibrium scheme is proposed for the aquated molybdocenes to provide a more complete picture of the aqueous speciation of the non- ansa molybdocene complexes, specifically by accounting for the third acidic proton in the titration curves and by describing the hydrolysis of Cp 2 MoO. Although the titration curve of the ansa -[C 2 Me 4 Cp 2 Mo(μ-OH)] 2 [OTs] 2 complex is different from that of [Cp 2 Mo(μ-OH)] 2 [OTs] 2 , 1 H NMR data suggest that the aqueous speciation of the ansa -[C 2 Me 4 Cp 2 Mo(μ-OH)] 2 [OTs] 2 complex is analogous to that of the non- ansa molybdocenes." @default.
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• W2090985831 date "2009-04-01" @default.
• W2090985831 modified "2023-09-26" @default.
• W2090985831 title "Aqueous Speciation of ansa- and non-ansa- Substituted [Cp2Mo(μ-OH)]2[OTs]2" @default.
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• W2090985831 doi "https://doi.org/10.1016/j.ica.2008.09.039" @default.
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