Zong Ruifa, Thummel Randolph P
Department of Chemistry, 136 Fleming Building, University of Houston, Houston, Texas 77204-5003, USA.
J Am Chem Soc. 2005 Sep 21;127(37):12802-3. doi: 10.1021/ja054791m.
Reaction of the bridging ligand 3,6-bis-[6'-(1' ',8' '-naphthyrid-2' '-yl)-pyrid-2'-yl]pyridazine (1) with [Ru(DMSO)4Cl2] in aqueous ethanol followed by excess 4-substituted pyridine (4-R-py) in the presence of triethylamine provides a series of three well-organized dinuclear complexes characterized by 1H NMR, MS, and X-ray. Mononuclear analogues are prepared from 4-tert-butyl-2,6-di(1',8'-naphthyrid-2'-yl)pyridine (5) and characterized in a similar fashion. All six complexes show electronic absorption and redox properties consistent with the electron donor/acceptor ability of the axial 4-R-py ligand. When an acetonitrile solution of the catalyst is added to an aqueous Ce(IV)-CF3SO3H solution (pH = 1.0) at 24 degrees C, oxygen evolution is observed for both mono and dinuclear systems. Turnover numbers range from 50 to 3200 with the best results being found when the axial ligand is 4-methylpyridine (mononuclear TN = 580 and dinuclear TN = 3200).
桥连配体3,6 - 双 - [6' - (1'',8'' - 萘啶 - 2'' - 基) - 吡啶 - 2' - 基]哒嗪(1)与[Ru(DMSO)₄Cl₂]在乙醇水溶液中反应，随后在三乙胺存在下加入过量的4 - 取代吡啶(4 - R - py)，得到了一系列经¹H NMR、质谱和X射线表征的结构规整的双核配合物。单核类似物由4 - 叔丁基 - 2,6 - 二(1',8' - 萘啶 - 2' - 基)吡啶(5)制备，并以类似方式进行表征。所有六种配合物的电子吸收和氧化还原性质均与轴向4 - R - py配体的电子供体/受体能力一致。当在24℃将催化剂的乙腈溶液加入到Ce(IV) - CF₃SO₃H水溶液(pH = 1.0)中时，单核和双核体系均观察到氧气析出。周转数范围为50至3200，当轴向配体为4 - 甲基吡啶时效果最佳(单核TN = 580，双核TN = 3200)。
