六磷杂戊搭烯笼状化合物P6C4tBu4与零价和二价铂配合物的简便插入和卤素迁移反应。

Facile insertion and halogen migration reactions of the hexaphosphapentaprismane cage P6C4tBu4 with zerovalent and divalent platinum complexes.

作者信息

Al-Ktaifani Mahmoud M, Hitchcock Peter B, Nixon John F

机构信息

Department of Chemistry, School of Life Sciences, University of Sussex, Falmer, Brighton, Sussex, UK BN1 9QJ.

出版信息

Dalton Trans. 2008 Mar 7(9):1132-5. doi: 10.1039/b719064f. Epub 2008 Jan 18.

DOI:10.1039/b719064f

PMID:18283372

Abstract

The hexaphosphapentaprismane P(6)C(4)(t)Bu(4) undergoes specific insertion of the zerovalent platinum fragment [Pt(PPh(3))(2)] into the unique P-P bond between the 5-membered rings to afford [Pt(PPh(3))(2)P(6)C(4)(t)Bu(4)]. A similar reaction with the Pt(ii) complexes [{PtCl(2)(PMe(3))}(2)] and [PtCl(2)(eta(4)-COD)] results in both insertion and chlorine migration reactions. The complexes [Pt(PPh(3))(2)P(6)C(4)(t)Bu(4)], trans-[PtCl(PMe(3))P(6)C(4)(t)Bu(4)Cl], cis-,trans-[{PtCl(2)(PMe(3))}micro-{P(6)C(4)(t)Bu(4)}{PtCl(2)(PMe(3))}], [{PtClP(6)C(4)(t)Bu(4)Cl}(2)] and cis-[PtClP(6)C(4)(t)Bu(4)Cl(P(6)C(4)(t)Bu(4))] have been structurally characterized by single crystal X-ray diffraction and multinuclear NMR studies.

摘要

六磷杂戊搭烯P(6)C(4)(t)Bu(4)经历了零价铂片段[Pt(PPh(3))(2)]特异性插入五元环之间独特的P-P键中，得到[Pt(PPh(3))(2)P(6)C(4)(t)Bu(4)]。与Pt(ii)配合物[{PtCl(2)(PMe(3))}(2)]和[PtCl(2)(η(4)-COD)]的类似反应会导致插入和氯迁移反应。配合物[Pt(PPh(3))(2)P(6)C(4)(t)Bu(4)]、反式-[PtCl(PMe(3))P(6)C(4)(t)Bu(4)Cl]、顺式,反式-[{PtCl(2)(PMe(3))}μ-{P(6)C(4)(t)Bu(4)}{PtCl(2)(PMe(3))}]、[{PtClP(6)C(4)(t)Bu(4)Cl}(2)]和顺式-[PtClP(6)C(4)(t)Bu(4)Cl(P(6)C(4)(t)Bu(4))]已通过单晶X射线衍射和多核NMR研究进行了结构表征。