Nakamura Go, Okamura Masaya, Yoshida Masaki, Suzuki Takayoshi, Takagi Hideo D, Kondo Mio, Masaoka Shigeyuki
Department of Structural Molecular Science, School of Physical Sciences, The Graduate University for Advanced Studies (SOKENDAI) , Shonan Village, Hayama-cho, Kanagawa 240-0193, Japan.
Inorg Chem. 2014 Jul 21;53(14):7214-26. doi: 10.1021/ic5003644. Epub 2014 Jun 25.
A series of phosphine-substituted ruthenium polypyridine complexes, cis(P,Cl)-[Ru(trpy)(Pqn)Cl]PF6 (cis-Cl), trans(P,MeCN)-Ru(trpy)(Pqn)(MeCN)2 (trans-PN), cis(P,MeCN)-Ru(trpy)(Pqn)(MeCN)2 (cis-PN), and Ru(trpy)(dppbz)(MeCN)2 (PP), were synthesized and crystallographically characterized (trpy = 2,2':6',2″-terpyridine, Pqn = 8-(diphenylphosphanyl)quinoline, and dppbz = 1,2-bis(diphenylphosphanyl)benzene). In electrochemical measurements for cis-PN and PP, the reduction of cis-PN resulted in the formation of trans-PN via cis-trans isomerization and that of PP proceeded via a two-electron-transfer reaction. The mechanism of the electrochemical behaviors is discussed through consideration of five-coordinated species, Ru(trpy)(Pqn) or Ru(trpy)(dppbz) (n = 0-2), formed by liberation of a monodentate labile ligand.
合成了一系列膦取代的钌多吡啶配合物，即顺式（P,Cl）-[Ru（trpy）（Pqn）Cl]PF6（顺式-Cl）、反式（P,MeCN）-Ru（trpy）（Pqn）（MeCN）2（反式-PN）、顺式（P,MeCN）-Ru（trpy）（Pqn）（MeCN）2（顺式-PN）和Ru（trpy）（dppbz）（MeCN）2（PP），并通过晶体学对其进行了表征（trpy = 2,2':6',2″-三联吡啶，Pqn = 8-（二苯基膦基）喹啉，dppbz = 1,2-双（二苯基膦基）苯）。在对顺式-PN和PP的电化学测量中，顺式-PN的还原通过顺反异构化导致反式-PN的形成，而PP的还原则通过双电子转移反应进行。通过考虑由单齿不稳定配体释放形成的五配位物种Ru（trpy）（Pqn）或Ru（trpy）（dppbz）（n = 0 - 2），讨论了电化学行为的机理。
