Academic Journal
Influence of triphosphine ligand coordination geometry in Mn(I) hydride complexes [(P∩P∩P)(CO) 2 MnH] on their kinetic hydricity
العنوان: | Influence of triphosphine ligand coordination geometry in Mn(I) hydride complexes [(P∩P∩P)(CO) 2 MnH] on their kinetic hydricity |
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المؤلفون: | Kovalenko, Sergey, A, Gulyaeva, Ekaterina, S, Osipova, Elena, S, Filippov, Oleg, A, Danshina, Anastasia, A, Vendier, Laure, Kireev, Nikolay, V, Godovikov, Ivan, A, Canac, Yves, Valyaev, Dmitry, A., Belkova, Natalia, V, Shubina, Elena, S |
المساهمون: | A. N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Russian Academy of Sciences Moscow (RAS), Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Russian Science Foundation, CNRS |
المصدر: | ISSN: 1477-9226. |
بيانات النشر: | HAL CCSD Royal Society of Chemistry |
سنة النشر: | 2024 |
المجموعة: | Université Toulouse III - Paul Sabatier: HAL-UPS |
مصطلحات موضوعية: | [CHIM.COOR]Chemical Sciences/Coordination chemistry |
الوصف: | International audience ; Octahedral Mn(I) complexes bearing tridentate donor ligands [(L∩L’∩L’’)(CO)2MnX] have recently emerged as major players in catalytic (de)hydrogenation processes. While most of these systems are still based on structurally rigid pincer scaffolds imposing a meridional coordination mode, for some more flexible tridentate ligands a facial arrangement of donor moieties becomes possible. Accordingly, the geometry of the corresponding Mn(I) hydrides [(L∩L’∩L’’)(CO)2MnH] directly involved in the catalytic processes, namely the nature of the donor extremity located in the trans-position of the hydride (CO and L for mer- and fac-configuration, respectively) may influence their hydride transfer ability. Herein, low-temperature IR and NMR spectroscopy studies of two model Mn(I) complexes mer-[(L1)(CO)2MnH] and fac-[(L2)(CO)2MnH] bearing similar triphosphine ligands (L1 = PhP(CH2CH2PPh2)2; L2 = MeC(CH2PPh2)3) in the presence of B(C6F5)3 as H− abstractor revealed for the first time a higher kinetic hydricity of the tripodal system. Even for the pincer complex, hydride transfer proceeds from the non-covalent adduct fac-[(L1)(CO)2MnH]∙∙∙B(C6F5)3 with facial geometry arising from the mer-to-fac isomerization of the initial mer-[(L1)(CO)2MnH]. The higher reactivity of the fac-hydride derivatives was found to be consistent with catalytic performance of the corresponding Mn(I) bromide complexes in the benchmark ester hydrosilylation. |
نوع الوثيقة: | article in journal/newspaper |
اللغة: | English |
DOI: | 10.1039/D4DT02496F |
الاتاحة: | https://hal.science/hal-04769905 https://hal.science/hal-04769905v1/document https://hal.science/hal-04769905v1/file/Kovalenko,%20Influence%20of%20triphosphine%20ligand%20coordination%20geometry,%202024.pdf https://doi.org/10.1039/D4DT02496F |
رقم الانضمام: | edsbas.EA2CD668 |
قاعدة البيانات: | BASE |
DOI: | 10.1039/D4DT02496F |
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