Assembly of a dihydrideborate and two aryl nitriles to form a C, N, N'-Pincer Ligand Coordinated to Osmium
| Autor: | Juan C. Babón, Ana M. López, Enrique Oñate, Israel Fernández, Miguel A. Esteruelas |
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| Přispěvatelé: | Ministerio de Ciencia, Innovación y Universidades (España), Agencia Estatal de Investigación (España), Ministerio de Economía y Competitividad (España), European Commission, Gobierno de Aragón |
| Rok vydání: | 2021 |
| Předmět: |
Valence (chemistry)
Nitrile 010405 organic chemistry Ligand Aryl Organic Chemistry 010402 general chemistry 01 natural sciences Oxidative addition 0104 chemical sciences Inorganic Chemistry Crystallography chemistry.chemical_compound chemistry Molecule Physical and Theoretical Chemistry Pincer ligand Natural bond orbital |
| Zdroj: | Zaguán: Repositorio Digital de la Universidad de Zaragoza Universidad de Zaragoza Digital.CSIC. Repositorio Institucional del CSIC instname Zaguán. Repositorio Digital de la Universidad de Zaragoza |
| Popis: | The C,N,N′-donor aryl-diimineborate pincer ligand of the complexes OsH2{κ3-C,N,N-[C6H3RCH═NB(cat)N═CHC6H4R]}(PiPr3)2 (R = H, Me) has been generated in a one-pot procedure, by the reaction of the hexahydride OsH6(PiPr3)2 with catecholborane (catBH) and two molecules of the corresponding aryl nitrile. The osmium–pincer bonding situation has been analyzed by means of atoms in molecules (AIM), natural bond orbital (NBO), and energy decomposition analysis coupled with the natural orbitals for chemical valence (EDA-NOCV) methods. According to the results, the complexes exhibit a rather strong electron-sharing Os–C bond, two weaker donor–acceptor N–Os bonds, and two π-back-donations from the transition metal to vacant π* orbitals of the formed metallacycles. In addition, spectroscopic findings and DFT calculations reveal that the donor units of the pincer are incorporated in a sequential manner. First, the central Os–N bond is formed, by the reaction of the dihydrideborate ligand of the intermediate OsH3{κ2-H,H-(H2Bcat)}(PiPr3)2 with one of the aryl nitriles. The subsequent oxidative addition of the o-C–H bond of the aryl substituent of the resulting κ1-N-(N-boryl-arylaldimine) affords the Os–C bond. Finally, the second Os–N bond is generated from a hydride, an ortho-metalated N-boryl-arylaldimine, and the second aryl nitrile. Financial support from the MINECO of Spain (Projects CTQ2017-82935-P (AEI/FEDER, UE), CTQ2016-78205-P, PID2019-106184GB-I00, and RED2018-102387-T), Gobierno de Aragón (Group E06_20R and project LMP148_18), FEDER, and the European Social Fund is acknowledged. |
| Databáze: | OpenAIRE |
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