Sterically Directed Functionalization of the Redox-Active Bis(imino)acenaphthene Ligand Class: An Experimental and Theoretical Investigation.
The synthesis, characterization, and theoretical study of the sterically directed functionalization of the redox-active bis(imino)acenaphthene (BIAN) ligand class has been explored. With dependence on the steric congestion encompassing the N-C-C-N fragment of the Ar-BIAN ligand, functionalization ca...
| Publicado en: | Journal of the American Chemical Society Vol. 135; no. 37; pp. 13939 - 13947 |
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| Autores principales: | , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
9/18/2013
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| Sumario: | The synthesis, characterization, and theoretical study of the sterically directed functionalization of the redox-active bis(imino)acenaphthene (BIAN) ligand class has been explored. With dependence on the steric congestion encompassing the N-C-C-N fragment of the Ar-BIAN ligand, functionalization can be directed to proceed either via a radical backbone dearomatization or a nucleophilic imine C-alkylation pathway. The structures of the Ar-BIAN derivatives 14-19 were determined by means of single-crystal X-ray diffraction. The reaction pathways involved in Ar-BIAN functionalization were monitored by means of EPR spectroscopy. The experimental results and observations were examined in conjunction with DFT-D calculations in order to explain the driving forces that direct the pathways leading to Ar-BIAN functionalization. |
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