Open Access
Molecules, volume 28, issue 8, pages 3368
The Dichotomy of Mn–H Bond Cleavage and Kinetic Hydricity of Tricarbonyl Manganese Hydride Complexes
Osipova Elena S
1
,
Kovalenko Sergey A
1
,
Gulyaeva Ekaterina S
1, 2
,
Kireev Nikolay V
1
,
Pavlov Alexander A.
1, 3
,
Filippov Oleg A.
1
,
Danshina Anastasia A.
1, 4
,
Valyaev D. A.
2
,
Canac Yves
2
,
shubina Elena S.
1
,
2
LCC-CNRS, Université de Toulouse, CNRS, 205 Route de Narbonne, CEDEX 4, 31077 Toulouse, France
|
Publication type: Journal Article
Publication date: 2023-04-11
PubMed ID:
37110601
Organic Chemistry
Drug Discovery
Physical and Theoretical Chemistry
Pharmaceutical Science
Molecular Medicine
Analytical Chemistry
Chemistry (miscellaneous)
Abstract
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.
Citations by journals
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1
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Russian Journal of Inorganic Chemistry
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Russian Journal of Inorganic Chemistry
1 publication, 33.33%
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Chemical Science
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Chemical Science
1 publication, 33.33%
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Chemistry - A European Journal
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Chemistry - A European Journal
1 publication, 33.33%
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1
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Citations by publishers
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1
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Pleiades Publishing
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Pleiades Publishing
1 publication, 33.33%
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Royal Society of Chemistry (RSC)
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Royal Society of Chemistry (RSC)
1 publication, 33.33%
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Wiley
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Wiley
1 publication, 33.33%
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1
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Osipova E. S. et al. The Dichotomy of Mn–H Bond Cleavage and Kinetic Hydricity of Tricarbonyl Manganese Hydride Complexes // Molecules. 2023. Vol. 28. No. 8. p. 3368.
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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. The Dichotomy of Mn–H Bond Cleavage and Kinetic Hydricity of Tricarbonyl Manganese Hydride Complexes // Molecules. 2023. Vol. 28. No. 8. p. 3368.
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TY - JOUR
DO - 10.3390/molecules28083368
UR - https://doi.org/10.3390%2Fmolecules28083368
TI - The Dichotomy of Mn–H Bond Cleavage and Kinetic Hydricity of Tricarbonyl Manganese Hydride Complexes
T2 - Molecules
AU - Osipova, Elena S
AU - Kovalenko, Sergey A
AU - Gulyaeva, Ekaterina S
AU - Kireev, Nikolay V
AU - Pavlov, Alexander A.
AU - Filippov, Oleg A.
AU - Danshina, Anastasia A.
AU - Valyaev, D. A.
AU - Canac, Yves
AU - shubina, Elena S.
AU - Belkova, Natalia V
PY - 2023
DA - 2023/04/11 00:00:00
PB - Multidisciplinary Digital Publishing Institute (MDPI)
SP - 3368
IS - 8
VL - 28
PMID - 37110601
SN - 1420-3049
ER -
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@article{2023_Osipova,
author = {Elena S Osipova and Sergey A Kovalenko and Ekaterina S Gulyaeva and Nikolay V Kireev and Alexander A. Pavlov and Oleg A. Filippov and Anastasia A. Danshina and D. A. Valyaev and Yves Canac and Elena S. shubina and Natalia V Belkova},
title = {The Dichotomy of Mn–H Bond Cleavage and Kinetic Hydricity of Tricarbonyl Manganese Hydride Complexes},
journal = {Molecules},
year = {2023},
volume = {28},
publisher = {Multidisciplinary Digital Publishing Institute (MDPI)},
month = {apr},
url = {https://doi.org/10.3390%2Fmolecules28083368},
number = {8},
pages = {3368},
doi = {10.3390/molecules28083368}
}
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MLA
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Osipova, Elena S., et al. “The Dichotomy of Mn–H Bond Cleavage and Kinetic Hydricity of Tricarbonyl Manganese Hydride Complexes.” Molecules, vol. 28, no. 8, Apr. 2023, p. 3368. https://doi.org/10.3390%2Fmolecules28083368.