The Dichotomy of Mn–H Bond Cleavage and Kinetic Hydricity of Tricarbonyl Manganese Hydride Complexes

Osipova, E.S.; Kovalenko, S.A.; Gulyaeva, E.S.; Kireev, N.V.; Pavlov, A.A.; Filippov, O.A.; Danshina, A.A.; Valyaev, D.A.; Canac, Y.; Shubina, E.S.; Belkova, N.V.

Авторы: Osipova Elena S., Kovalenko Sergey A., Gulyaeva Ekaterina S., Kireev Nikolay V., Pavlov Alexander A., Filippov Oleg A., Danshina Anastasia A., Valyaev Dmitry A., Canac Yves, Shubina Elena S., Belkova Natalia V.
Журнал: Molecules
Том: 28
Номер: 8
Год издания: 2023
Издательство: MDPI
Местоположение издательства: Basel, Switzerland
Номер статьи: 3368
DOI: 10.3390/molecules28083368
Аннотация: Acid-base characteristics (acidity, pKa, and hydricity, ΔG°H− or kH−) of metal hydride complexes could be a helpful value for forecasting their activity in various catalytic reactions. Polarity of the M–H bond may change radically at the stage of formation of a non-covalent adduct with an acidic/basic partner. This stage is responsible for subsequent hydrogen ion (hydride or proton) transfer. Here, the reaction of tricarbonyl manganese hydrides mer,trans–[L2Mn(CO)3H] (1; L = P(OPh)3, 2; L = PPh3) and fac–[(L–L′)Mn(CO)3H] (3, L–L′ = Ph2PCH2PPh2 (dppm); 4, L–L′ = Ph2PCH2–NHC) with organic bases and Lewis acid (B(C6F5)3) was explored by spectroscopic (IR, NMR) methods to find the conditions for the Mn–H bond repolarization. Complex 1, bearing phosphite ligands, features acidic properties (pKa 21.3) but can serve also as a hydride donor (ΔG≠298K = 19.8 kcal/mol). Complex 3 with pronounced hydride character can be deprotonated with KHMDS at the CH2–bridge position in THF and at the Mn–H position in MeCN. The kinetic hydricity of manganese complexes 1–4 increases in the order mer,trans–[(P(OPh)3)2Mn(CO)3H] (1) < mer,trans–[(PPh3)2Mn(CO)3H] (2) ≈ fac–[(dppm)Mn(CO)3H] (3) < fac–[(Ph2PCH2NHC)Mn(CO)3H] (4), corresponding to the gain of the phosphorus ligand electron-donor properties
Добавил в систему: Шубина Елена Соломоновна

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The Dichotomy of Mn–H Bond Cleavage and Kinetic Hydricity of Tricarbonyl Manganese Hydride Complexesстатья

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