Synthesis and coordination chemistry of a 14-membered macrocyclic ligand containing one phosphorus, two sulfur and one ambidentate sulfoxide donor sets
作者:Pak-Hing Leung、Anming Liu、K. F. Mok、Andrew J. P. White、David J. Williams
DOI:10.1039/a900264b
日期:——
atoms giving the corresponding neutral square-planar complexes cis-[M(L-P,S)Cl2]. In both complexes, the sulfoxide group is not involved in metal complexation. However, when the dichloro complexes were treated with silver perchlorate, the corresponding tetradentate complexes [ML-P,S,S,S}][ClO4]2 were formed. In both the perchlorate salts, the ambidentate sulfoxide functions are coordinated to the metal
大环配体PhP(CH 2 CH 2 SCH 2 CH 2 CH 2)2 SO(L)由双(3-氯丙基)亚砜与双(2-巯基乙基)苯基膦在碳酸铯存在下的反应获得。配体在固态中稳定,但在溶液中缓慢重排成异构的氧化膦S(CH 2 CH 2 CH 2 SCH 2 CH 2)2 P(O)Ph。在分子碘存在下,氧迁移过程自发发生,并在几分钟内定量获得氧化膦。当用[MCl2(CH 3 CN) 2 ](其中M = Pd,Pt),亚磺酰基取代的大环通过其磷和一个硫醚硫供体原子之一,作为二齿配体,给出相应的中性方平面配合物顺式-[M] (L- P,S)Cl 2 ]。在两种配合物中,亚砜基均不参与金属配合。然而,当用高氯酸银处理二氯配合物时,相应的四齿配合物[M L- P, S, S, S }] [ClO 4 ] 2形成了。在两种高氯酸盐中,环境性亚砜官能团均通过其硫供体与金属中心配位。与先前报道的无环类似物相反,亚砜-金属键在动力学上是稳定的。