Reactivity of a T-shaped cobalt(i ) pincer-complex
| Autor: | Lutz H. Gade, Clemens K. Blasius, Hubert Wadepohl, Regina Matveeva |
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| Rok vydání: | 2021 |
| Předmět: | |
| Zdroj: | Dalton Transactions. 50:6802-6810 |
| ISSN: | 1477-9234 1477-9226 |
| DOI: | 10.1039/d1dt00277e |
| Popis: | The reactivity of a paramagnetic T-shaped cobalt(i) complex, [(iPrboxmi)Co], stabilised by a monoanionic bis(oxazolinylmethylidene)-isoindolate (boxmi) NNN pincer ligand is described. The exposure to carbon monoxide as an additional neutral ligand resulted in the square-planar species [(iPrboxmi)Co(CO)], accompanied by a change in the electronic spin state from S = 1 to S = 0. In contrast, upon treatment with trimethylphosphine the formation of the distorted tetrahedral complex [(iPrboxmi)Co(PMe3)] was observed (S = 1). Reacting [(iPrboxmi)Co] with iodine (I2), organic peroxides (tBu2O2, (SiMe3)2O2) and diphenyldisulphide (Ph2S2) yielded the tetracoordinated complexes [(iPrboxmi)CoI], [(iPrboxmi)Co(OtBu)], [(iPrboxmi)Co(OSiMe3)] and [(iPrboxmi)Co(SPh)], respectively, demonstrating the capability of the boxmi-supported cobalt(i) complex to homolytically cleave bonds and thus its distinct one-electron reactivity. Furthermore, a square-planar cobalt(ii) alkynyl complex [(iPrboxmi)Co(CCArF)] was identified as the main product in the reaction between [(iPrboxmi)Co] and a terminal alkyne, 4-fluoro-1-ethynylbenzene. Putting such species in the context of the previously investigated hydroboration catalysis, its stoichiometric reaction with pinacolborane revealed its potential conversion into a cobalt(ii) hydride complex, thus confirming its original attribution as off-cycle species. |
| Databáze: | OpenAIRE |
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