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

التفاصيل البيبلوغرافية
العنوان: The Dichotomy of Mn-H Bond Cleavage and Kinetic Hydricity of Tricarbonyl Manganese Hydride Complexes.
المؤلفون: Osipova ES; A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), 28, Vavilova Str., 119334 Moscow, Russia., Kovalenko SA; A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), 28, Vavilova Str., 119334 Moscow, Russia., Gulyaeva ES; A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), 28, Vavilova Str., 119334 Moscow, Russia.; LCC-CNRS, Université de Toulouse, CNRS, 205 Route de Narbonne, CEDEX 4, 31077 Toulouse, France., Kireev NV; A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), 28, Vavilova Str., 119334 Moscow, Russia., Pavlov AA; A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), 28, Vavilova Str., 119334 Moscow, Russia.; Center of National Technological Initiative, Bauman Moscow State Technical University, 2nd Baumanskaya Str., 5, 105005 Moscow, Russia., Filippov OA; A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), 28, Vavilova Str., 119334 Moscow, Russia., Danshina AA; A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), 28, Vavilova Str., 119334 Moscow, Russia.; Moscow Institute of Physics and Technology, Institutskiy per., 9, 141700 Dolgoprudny, Russia., Valyaev DA; LCC-CNRS, Université de Toulouse, CNRS, 205 Route de Narbonne, CEDEX 4, 31077 Toulouse, France., Canac Y; LCC-CNRS, Université de Toulouse, CNRS, 205 Route de Narbonne, CEDEX 4, 31077 Toulouse, France., Shubina ES; A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), 28, Vavilova Str., 119334 Moscow, Russia., Belkova NV; A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), 28, Vavilova Str., 119334 Moscow, Russia.
المصدر: Molecules (Basel, Switzerland) [Molecules] 2023 Apr 11; Vol. 28 (8). Date of Electronic Publication: 2023 Apr 11.
نوع المنشور: Journal Article
اللغة: English
بيانات الدورية: Publisher: MDPI Country of Publication: Switzerland NLM ID: 100964009 Publication Model: Electronic Cited Medium: Internet ISSN: 1420-3049 (Electronic) Linking ISSN: 14203049 NLM ISO Abbreviation: Molecules Subsets: PubMed not MEDLINE; MEDLINE
أسماء مطبوعة: Original Publication: Basel, Switzerland : MDPI, c1995-
مستخلص: Acid-base characteristics (acidity, p K a, and hydricity, ΔG° H- or k H- ) 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 -[L 2 Mn(CO) 3 H] ( 1 ; L = P(OPh) 3 , 2 ; L = PPh 3 ) and fac -[(L-L')Mn(CO) 3 H] ( 3 , L-L' = Ph 2 PCH 2 PPh 2 (dppm); 4 , L-L' = Ph 2 PCH 2 -NHC) with organic bases and Lewis acid (B(C 6 F 5 ) 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 (p K a 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 CH 2 -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 ) 2 Mn(CO) 3 H] ( 1 ) < mer , trans -[(PPh 3 ) 2 Mn(CO) 3 H] ( 2 ) ≈ fac -[(dppm)Mn(CO) 3 H] ( 3 ) < fac -[(Ph 2 PCH 2 NHC)Mn(CO) 3 H] ( 4 ), corresponding to the gain of the phosphorus ligand electron-donor properties.
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معلومات مُعتمدة: 22-73-00072 Russian Science Foundation
فهرسة مساهمة: Keywords: hydricity; hydride transfer; hydrogen bond; manganese hydrides; non-covalent interactions; proton transfer
تواريخ الأحداث: Date Created: 20230428 Date Completed: 20230430 Latest Revision: 20230501
رمز التحديث: 20230501
مُعرف محوري في PubMed: PMC10143952
DOI: 10.3390/molecules28083368
PMID: 37110601
قاعدة البيانات: MEDLINE
الوصف
تدمد:1420-3049
DOI:10.3390/molecules28083368