Bonding and Reactivity of a Pair of Neutral and Cationic Heterobimetallic RuZn2 Complexes
| Autor: | Lia Sotorríos, Mary F. Mahon, Nasir A. Rajabi, Anne-Frédérique Pécharman, Michael K. Whittlesey, Stuart MacGregor, John P. Lowe, Fedor M. Miloserdov |
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| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
010405 organic chemistry
Ligand Chemistry Thermal decomposition Organic Chemistry Cationic polymerization 010402 general chemistry 01 natural sciences Medicinal chemistry Organische Chemie 3. Good health 0104 chemical sciences Inorganic Chemistry IMes chemistry.chemical_compound Life Science Reactivity (chemistry) Lewis acids and bases Physical and Theoretical Chemistry Phosphine |
| Zdroj: | Inorganic Chemistry 60 (2021) 21 Inorganic Chemistry, 60(21), 16256-16265 |
| ISSN: | 0020-1669 |
| DOI: | 10.1021/acs.inorgchem.1c02072 |
| Popis: | A combined experimental and computational study of the structure and reactivity of two [RuZn2Me2] complexes, neutral [Ru(PPh3)(Ph2PC6H4)2(ZnMe)2] (2) and cationic [Ru(PPh3)2(Ph2PC6H4)(ZnMe)2][BArF4] ([BArF4] = [B{3,5-(CF3)2C6H3}4]) (3), is presented. Structural and computational analyses indicate these complexes are best formulated as containing discrete ZnMe ligands in which direct Ru–Zn bonding is complemented by weaker Zn···Zn interactions. The latter are stronger in 2, and both complexes exhibit an additional Zn···Caryl interaction with a cyclometalated phosphine ligand, this being stronger in 3. Both 2 and 3 show diverse reactivity under thermolysis and with Lewis bases (PnBu3, PCy3, and IMes). With 3, all three Lewis bases result in the loss of [ZnMe]+. In contrast, 2 undergoes PPh3 substitution with PnBu3, but with IMes, loss of ZnMe2 occurs to form [Ru(PPh3)(C6H4PPh2)(C6H4PPhC6H4Zn(IMes))H] (7). The reaction of 3 with H2 affords the cationic trihydride complex [Ru(PPh3)2(ZnMe)2(H)3][BArF4] (12). Computational analyses indicate that both 12 and 7 feature bridging hydrides that are biased toward Ru over Zn. |
| Databáze: | OpenAIRE |
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