title: Pi-bonded quinonoid transition-metal complexes.
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.
authors.affiliation: Department of Chemistry, Brown University, Providence, RI 02912, USA.
authors.forename: Jeffrey A
authors.initials: JA
authors.lastname: Reingold
authors.forename: Seung
authors.initials: S
authors.lastname: Uk Son
authors.forename: Sang
authors.initials: S
authors.lastname: Bok Kim
authors.forename: Conor A
authors.initials: CA
authors.lastname: Dullaghan
authors.forename: Moonhyun
authors.initials: M
authors.lastname: Oh
authors.forename: Paul C
authors.initials: PC
authors.lastname: Frake
authors.forename: Gene B
authors.initials: GB
authors.lastname: Carpenter
authors.forename: Dwight A
authors.initials: DA
authors.lastname: Sweigart
mesh_terms: D002384:Catalysis; D006873:Hydroquinones / Q000737:chemistry*; D045563:Indolequinones / Q000737:chemistry; D008345:Manganese / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D053758:Nanoparticles / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry; D028561:Transition Elements / Q000737:chemistry*
chemical_list: D006873:Hydroquinones; D045563:Indolequinones; D009942:Organometallic Compounds; D028561:Transition Elements; C068040:quinone methide; D008345:Manganese; D012238:Rhodium