Reingold Jeffrey A, Uk Son Seung, Bok Kim Sang, Dullaghan Conor A, Oh Moonhyun, Frake Paul C, Carpenter Gene B, Sweigart Dwight A
Department of Chemistry, Brown University, Providence, RI 02912, USA.
Dalton Trans. 2006 May 28(20):2385-98. doi: 10.1039/b602678h. Epub 2006 Apr 24.
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.
对苯二酚的碳环与亲电过渡金属片段（如Mn(CO)₃⁺和Rh(COD)⁺）配位会生成稳定的π键η⁶配合物，这些配合物可被激活，使-OH基团易于发生可逆去质子化。去质子化过程伴随着电子转移至过渡金属，过渡金属充当内部氧化剂或电子受体。以锰作为金属时，生成的η⁵-半醌和η⁴-醌配合物已被用于合成一维、二维和三维聚合物金属-有机金属配位网络。以铑作为金属时，π-醌类配合物已被证明在多功能C-C偶联催化以及新型有机锂试剂的合成中发挥独特作用。这两类π-醌类配合物似乎在纳米化学中具有重要应用，因为它们为将纳米颗粒定向自组装成功能材料提供了出色的模板载体。
