Pi-bonded quinonoid transition-metal complexes |
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Authors: | Reingold Jeffrey A Uk Son Seung Bok Kim Sang Dullaghan Conor A Oh Moonhyun Frake Paul C Carpenter Gene B Sweigart Dwight A |
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Affiliation: | Department of Chemistry, Brown University, Providence, RI 02912, USA. |
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Abstract: | Coordination of the carbocyclic ring of hydroquinones to electrophilic transition-metal fragments such as Mn(CO)3+ and Rh(COD)+ produces stable pi-bonded eta6-complexes that are activated to facile reversible deprotonation of the -OH groups. The deprotonations are accompanied by electron transfer to the transition metal, which acts as an internal oxidizing agent or electron sink. With manganese as the metal, the resulting eta5-semiquinone and eta4-quinone complexes have been used to synthesize one- two- and three-dimensional polymeric metal-organometallic coordination networks. With rhodium as the metal, the pi-quinonoid complexes have been demonstrated to play a unique role in multifunctional C-C coupling catalysis and in the synthesis of new organolithium reagents. Both classes of pi-quinonoid complexes appear to have significant applications in nanochemistry by providing an excellent vehicle for templating the directed self-assembly of nanoparticles into functional materials. |
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