Oxygenextrusion from amidate ligands to generate terminal TaO units under reducing conditions. How to successfully use amidate ligands in dinitrogen coordination chemistry
| Autor: | Patricia Horrillo-Martinez, Michael D. Fryzuk, Brian O. Patrick, Laurel L. Schafer |
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| Rok vydání: | 2012 |
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| Zdroj: | Dalton Trans.. 41:1609-1616 |
| ISSN: | 1477-9234 1477-9226 |
| DOI: | 10.1039/c1dt11595b |
| Popis: | A series of mixed Cp* amidate tantalum complexes Cp*Ta(RNC(O)R')X(3) (where R = Me(2)C(6)H(3), (i)Pr, R' = (t)Bu, Ph, X = Cl, Me) have been prepared via salt metathesis and their fundamental reactivities under reducing conditions have been explored. Reaction of the tantalum chloro precursors with potassium graphite under N(2) or Ar leads to the stereoselective formation of the terminal tantalum oxo species, Cp*Ta=O(η(2)-RN=CR')Cl. This represents the formal extrusion of oxygen from the amidate ligand to the reduced tantalum center and is accompanied by the formation of the iminoacyl fragment bound to Ta(v). Amidate dinitrogen complexes, [Cp*TaCl(RNC(O)(t)Bu)](2)(μ-N(2)) (where R = Me(2)C(6)H(3), (i)Pr) were synthesized via salt metathesis from the known [Cp*TaCl(2)](2)(μ-N(2)) precursor, establishing that amidate ligands can support dinitrogen complexes, but not the reduction process often necessary for their synthesis. |
| Databáze: | OpenAIRE |
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