Tridentate ligands with [P,N,O] donor sets, prepared either by the condensation of 2-(diphenylphosphino)benzaldehyde with 1S,2R-norephedrine (HL1) or 2-aminophenol (HL2) or by the condensation of 2-(diphenylphosphino)aniline with salicylaldehyde (sal) (HL3), 5-(NO2)sal (HL4), 5-(Cl)sal (HL5), 5-(Br)sal (HL6), 5-(MeO)sal (HL7) or 3-(MeO)sal (HL8), reacted with [RuIICl2(dmso)4] in refluxing thf solution to yield complexes of the general formula cis-[RuIICl(η3-L1–8)(dmso)2]. Use of two equivalents of ligand HL1 resulted in the formation of mer-[RuII(η3-L1)2], a reaction not seen for HL2–8. Aerial oxidation of cis,mer-[RuIICl(η3-L3)(dmso)2] in a chloroform solution yielded cis,fac-[RuIIICl2(η3-L3)(dmso)], which has undergone an unexpected rearrangement of co-ordination geometry.
具有 [P,N,O] 供体组的三齿
配体,通过 2-(
二苯基膦)
苯甲醛与 1S,2R-
去甲麻黄碱 (HL1) 或
2-氨基苯酚 (H
L2) 缩合或通过 2-(
二苯基膦) 缩合制备)
苯胺与
水杨醛(sal) (HL3)、5-(
NO2)sal (HL4)、5-(Cl)sal (HL5)、5-(Br)sal (HL6)、5-(MeO)sal (HL7)或 3-(MeO)sal (HL8),在回流 thf 溶液中与 [RuIIC
L2(dmso)4] 反应,生成通式 cis-[RuIICl(η3-L1–8)(dmso)2] 的络合物。使用两当量的
配体 HL1 导致形成 mer-[RuII(η3-L1)2],这是 H
L2-8 中未见的反应。在
氯仿溶液中对 cis,mer-[RuIICl(η3-L3)(dmso)2] 进行空气氧化,得到 cis,fac-[RuIIIC
L2(η3-L3)(dmso)],其发生了意想不到的配位重排几何学。