与半不稳定螯合配体自发形成杂配位的PtII配合物。

Spontaneous formation of heteroligated PtII complexes with chelating hemilabile ligands.

作者信息

Ulmann Pirmin A, Brown Aaron M, Ovchinnikov Maxim V, Mirkin Chad A, DiPasquale Antonio G, Rheingold Arnold L

机构信息

Department of Chemistry and the International Institute for Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113, USA.

出版信息

Chemistry. 2007;13(16):4529-34. doi: 10.1002/chem.200601837.

DOI:10.1002/chem.200601837

PMID:17393545

Abstract

The spontaneous formation of the heteroligated complex [PtCl(kappa(2)-Ph(2)PCH(2)CH(2)SMe)(Ph(2)PCH(2)CH(2)SPh)]Cl (8 a) by a novel ligand rearrangement process has been observed. By using the weak-link approach, the relative arrangement of the alkyl and aryl groups can be controlled by abstraction of chloride from 8 a to form the closed complex [Pt(kappa(2)-Ph(2)PCH(2)CH(2)SMe)(kappa(2)-Ph(2)PCH(2)CH(2)SPh)]BF(4) (5) and reopening using halide ions to form semi-open complexes [PtX(kappa(2)-Ph(2)PCH(2)CH(2)SMe)(Ph(2)PCH(2)CH(2)SPh)]BF(4) (8 b; X=Cl(-)) and (8 c; X=I(-)). Analogous procedures using Ph(2)PCH(2)CH(2)SMe and 1,4-(Ph(2)PCH(2)CH(2)S)(2)C(6)H(4) lead to heteroligated bimetallic complexes 7 and 9, illustrating that this ligand rearrangement process can be used as a tool for the assembly of complementary metallosupramolecular structures.

摘要

通过一种新型配体重排过程，已观察到杂配络合物[PtCl(κ(2)-Ph(2)PCH(2)CH(2)SMe)(Ph(2)PCH(2)CH(2)SPh)]Cl (8 a)的自发形成。通过使用弱键方法，烷基和芳基的相对排列可通过从8 a中提取氯离子来控制，以形成封闭络合物[Pt(κ(2)-Ph(2)PCH(2)CH(2)SMe)(κ(2)-Ph(2)PCH(2)CH(2)SPh)]BF(4) (5)，然后使用卤离子重新打开以形成半开放络合物[PtX(κ(2)-Ph(2)PCH(2)CH(2)SMe)(Ph(2)PCH(2)CH(2)SPh)]BF(4) (8 b; X = Cl(-))和(8 c; X = I(-))。使用Ph(2)PCH(2)CH(2)SMe和1,4-(Ph(2)PCH(2)CH(2)S)(2)C(6)H(4)的类似程序会导致杂配双金属络合物7和9的形成，这表明这种配体重排过程可作为组装互补金属超分子结构的一种工具。