Unique Radical Dearomatization and Two-Electron Reduction of a Redox-Active Ligand

The syntheses and characterizations of [Li₄]­[(1,2-di-(<i>tert</i>-butyl)-dpp-BIAN)₂] (<b>7</b>), (1,2-di-(<i>tert</i>-butyl)-dpp-BIAN) (<b>8</b>), and (1-(<i>tert</i>-butyl)-2-OH-dpp-BIAN) (<b>9</b>) are described. Compound <b>7</b> was formed via a radical dearomatization, two-electron reduction pathway that was accompanied by vicinal di-<i>tert</i>-butylation of the BIAN ligand backbone. Oxidation of <b>7</b> afforded a dearomatized vicinal di-<i>tert</i>-butyl substituted BIAN ligand (<b>8</b>). An analogous dearomatized vicinal <i>tert</i>-butyl-hydroxy substituted BIAN ligand (<b>9</b>) was also isolated in the course of mechanistic studies related to the formation of <b>7</b>

Unique Radical Dearomatization and Two-Electron Reduction of a Redox-Active Ligand

The syntheses and characterizations of [Li₄]­[(1,2-di-(<i>tert</i>-butyl)-dpp-BIAN)₂] (<b>7</b>), (1,2-di-(<i>tert</i>-butyl)-dpp-BIAN) (<b>8</b>), and (1-(<i>tert</i>-butyl)-2-OH-dpp-BIAN) (<b>9</b>) are described. Compound <b>7</b> was formed via a radical dearomatization, two-electron reduction pathway that was accompanied by vicinal di-<i>tert</i>-butylation of the BIAN ligand backbone. Oxidation of <b>7</b> afforded a dearomatized vicinal di-<i>tert</i>-butyl substituted BIAN ligand (<b>8</b>). An analogous dearomatized vicinal <i>tert</i>-butyl-hydroxy substituted BIAN ligand (<b>9</b>) was also isolated in the course of mechanistic studies related to the formation of <b>7</b>

Unique Radical Dearomatization and Two-Electron Reduction of a Redox-Active Ligand

The syntheses and characterizations of [Li₄]­[(1,2-di-(<i>tert</i>-butyl)-dpp-BIAN)₂] (<b>7</b>), (1,2-di-(<i>tert</i>-butyl)-dpp-BIAN) (<b>8</b>), and (1-(<i>tert</i>-butyl)-2-OH-dpp-BIAN) (<b>9</b>) are described. Compound <b>7</b> was formed via a radical dearomatization, two-electron reduction pathway that was accompanied by vicinal di-<i>tert</i>-butylation of the BIAN ligand backbone. Oxidation of <b>7</b> afforded a dearomatized vicinal di-<i>tert</i>-butyl substituted BIAN ligand (<b>8</b>). An analogous dearomatized vicinal <i>tert</i>-butyl-hydroxy substituted BIAN ligand (<b>9</b>) was also isolated in the course of mechanistic studies related to the formation of <b>7</b>

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 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 <b>14</b>–<b>19</b> 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

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 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 <b>14</b>–<b>19</b> 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

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 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 <b>14</b>–<b>19</b> 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

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 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 <b>14</b>–<b>19</b> 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

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 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 <b>14</b>–<b>19</b> 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

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 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 <b>14</b>–<b>19</b> 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

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 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 <b>14</b>–<b>19</b> 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