Synthesis of a carborane-substituted bis(phosphanido) cobaltate(i ), ligand substitution, and unusual P4 fragmentation
| Autor: | Peter Coburger, Daniel J. Scott, Evamarie Hey-Hawkins, Robert Wolf, Gabriele Hierlmeier, Ilya G. Shenderovich, Julia Leitl |
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| Rok vydání: | 2021 |
| Předmět: |
010405 organic chemistry
Phosphaalkyne Ligand ddc:540 chemistry.chemical_element General Chemistry 010402 general chemistry 01 natural sciences Medicinal chemistry Oxidative addition 3. Good health 0104 chemical sciences chemistry.chemical_compound chemistry 540 Chemie Carborane Single bond Moiety Cobalt Cyclooctadiene |
| Zdroj: | Chemical Science, 12 (33) Chemical Science |
| ISSN: | 2041-6539 2041-6520 |
| DOI: | 10.1039/d1sc02948g |
| Popis: | Oxidative addition of the P-P single bond of an ortho-carborane-derived 1,2-diphosphetane (1,2-C-2(PMes)(2)B10H10) (Mes = 2,4,6-Me3C6H2) to cobalt(-i) and nickel(0) sources affords the first heteroleptic complexes of a carborane-bridged bis(phosphanido) ligand. The complexes also incorporate labile ligands suitable for further functionalisation. Thus, the cobalt(i) complex [K([18]crown-6)][Co{1,2-(PMes)(2)C2B10H10}(cod)] (cod = 1,5-cyclooctadiene) bearing a labile cyclooctadiene ligand undergoes facile ligand exchange reactions with isonitriles and tert-butyl phosphaalkyne with retention of the bis(phosphanido) ligand. However, in the reaction with one equivalent of P-4, the electron-rich bis(phosphanido) moiety abstracts a single phosphorus atom with formation of a new P-3 chain, while the remaining three P atoms derived from P-4 form an eta(3)-coordinating cyclo-P-3 ligand. In contrast, when the same reaction is performed with two equivalents of the cobalt(i) complex, a dinuclear product is formed which features an unusual P-4 chain in its molecular structure. Chemical Science, 12 (33) ISSN:2041-6520 ISSN:2041-6539 |
| Databáze: | OpenAIRE |
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