{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,4]],"date-time":"2026-04-04T15:24:51Z","timestamp":1775316291584,"version":"3.50.1"},"reference-count":41,"publisher":"MDPI AG","issue":"8","license":[{"start":{"date-parts":[[2023,4,11]],"date-time":"2023-04-11T00:00:00Z","timestamp":1681171200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100006769","name":"Russian Science Foundation","doi-asserted-by":"publisher","award":["22-73-00072"],"award-info":[{"award-number":["22-73-00072"]}],"id":[{"id":"10.13039\/501100006769","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Acid-base characteristics (acidity, pKa, and hydricity, \u0394G\u00b0H\u2212 or kH\u2212) of metal hydride complexes could be a helpful value for forecasting their activity in various catalytic reactions. Polarity of the M\u2013H 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\u2013[L2Mn(CO)3H] (1; L = P(OPh)3, 2; L = PPh3) and fac\u2013[(L\u2013L\u2032)Mn(CO)3H] (3, L\u2013L\u2032 = Ph2PCH2PPh2 (dppm); 4, L\u2013L\u2032 = Ph2PCH2\u2013NHC) with organic bases and Lewis acid (B(C6F5)3) was explored by spectroscopic (IR, NMR) methods to find the conditions for the Mn\u2013H bond repolarization. Complex 1, bearing phosphite ligands, features acidic properties (pKa 21.3) but can serve also as a hydride donor (\u0394G\u2260298K = 19.8 kcal\/mol). Complex 3 with pronounced hydride character can be deprotonated with KHMDS at the CH2\u2013bridge position in THF and at the Mn\u2013H position in MeCN. The kinetic hydricity of manganese complexes 1\u20134 increases in the order mer,trans\u2013[(P(OPh)3)2Mn(CO)3H] (1) &lt; mer,trans\u2013[(PPh3)2Mn(CO)3H] (2) \u2248 fac\u2013[(dppm)Mn(CO)3H] (3) &lt; fac\u2013[(Ph2PCH2NHC)Mn(CO)3H] (4), corresponding to the gain of the phosphorus ligand electron-donor properties.<\/jats:p>","DOI":"10.3390\/molecules28083368","type":"journal-article","created":{"date-parts":[[2023,4,12]],"date-time":"2023-04-12T02:08:11Z","timestamp":1681265291000},"page":"3368","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["The Dichotomy of Mn\u2013H Bond Cleavage and Kinetic Hydricity of Tricarbonyl Manganese Hydride Complexes"],"prefix":"10.3390","volume":"28","author":[{"given":"Elena S.","family":"Osipova","sequence":"first","affiliation":[{"name":"A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), 28, Vavilova Str., 119334 Moscow, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Sergey A.","family":"Kovalenko","sequence":"additional","affiliation":[{"name":"A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), 28, Vavilova Str., 119334 Moscow, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ekaterina S.","family":"Gulyaeva","sequence":"additional","affiliation":[{"name":"A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), 28, Vavilova Str., 119334 Moscow, Russia"},{"name":"LCC-CNRS, Universit\u00e9 de Toulouse, CNRS, 205 Route de Narbonne, CEDEX 4, 31077 Toulouse, France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Nikolay V.","family":"Kireev","sequence":"additional","affiliation":[{"name":"A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), 28, Vavilova Str., 119334 Moscow, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Alexander A.","family":"Pavlov","sequence":"additional","affiliation":[{"name":"A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), 28, Vavilova Str., 119334 Moscow, Russia"},{"name":"Center of National Technological Initiative, Bauman Moscow State Technical University, 2nd Baumanskaya Str., 5, 105005 Moscow, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7963-2806","authenticated-orcid":false,"given":"Oleg A.","family":"Filippov","sequence":"additional","affiliation":[{"name":"A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), 28, Vavilova Str., 119334 Moscow, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0368-2177","authenticated-orcid":false,"given":"Anastasia A.","family":"Danshina","sequence":"additional","affiliation":[{"name":"A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), 28, Vavilova Str., 119334 Moscow, Russia"},{"name":"Moscow Institute of Physics and Technology, Institutskiy per., 9, 141700 Dolgoprudny, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1772-844X","authenticated-orcid":false,"given":"Dmitry A.","family":"Valyaev","sequence":"additional","affiliation":[{"name":"LCC-CNRS, Universit\u00e9 de Toulouse, CNRS, 205 Route de Narbonne, CEDEX 4, 31077 Toulouse, France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3747-554X","authenticated-orcid":false,"given":"Yves","family":"Canac","sequence":"additional","affiliation":[{"name":"LCC-CNRS, Universit\u00e9 de Toulouse, CNRS, 205 Route de Narbonne, CEDEX 4, 31077 Toulouse, France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8057-3703","authenticated-orcid":false,"given":"Elena S.","family":"Shubina","sequence":"additional","affiliation":[{"name":"A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), 28, Vavilova Str., 119334 Moscow, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9346-8208","authenticated-orcid":false,"given":"Natalia V.","family":"Belkova","sequence":"additional","affiliation":[{"name":"A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), 28, Vavilova Str., 119334 Moscow, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2023,4,11]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"191","DOI":"10.1016\/j.ccr.2015.06.015","article-title":"Manganese organometallic compounds in homogeneous catalysis: Past, present, and prospects","volume":"308","author":"Valyaev","year":"2016","journal-title":"Coord. Chem. 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