Preparation of Dimethyl and Chloro/Methyl Complexes of Platinum(II) Supported byα-Diimine Ligands: Trends in the Ease of Oxidation to Platinum(IV)
作者:John D. Scollard、Mike Day、Jay A. Labinger、John E. Bercaw
DOI:10.1002/1522-2675(20011017)84:10<3247::aid-hlca3247>3.0.co;2-w
日期:2001.10.17
first-order each in [PtII], [PtIV] and [I−]. Oxidation by a one-electron process in MeCN solution results in a rapid subsequent disproportionation to PtIIMe and PtIVMe3 cations with MeCN occupying the fourth or sixth coordination sites. Single-crystal X-ray structure determinations for [(2,6-Me2PhDABMe)PtMe3(MeCN)]+[PtCl6]0.5(MeCN) and [(CyDABH)PtMe3(MeCN)]+[PtCl6]0.5(MeCN) are reported.
α-二亚胺配体与铂 (II) 烷基配合物 [(Me2S)PtMe2]2 和 (Me2S)2PtClMe 反应形成 (RDABR')PtMe2 和 (RDABR')PtClMe (RDABR'=RN=CR'-CR'= NR;R=2,6-Me2Ph、2,6-(CHMe2)2Ph、3,5-Me2Ph、3,5-(CF3)2Ph、C6H11;R'=Me、H)。已经研究了这些配合物与 Cl2、I2、N-氯代琥珀酰亚胺、[PtCl6]2- 和 (TMEDA)PtMe2I2 的氧化。试图以电化学方式确定 PtII 配合物的氧化电位仅产生不可逆的单电子氧化。然而,已经确定了 (RDABR')PtMe2<(RDABR')PtClMe<(RDABR')PtCl2≪(RDABR')PtMe(solvent)]+ 系列的氧化难度增加的定性排序。氧化通过桥接双核中间体的双电子内球电子转移进行。(TMEDA)PtMe2I2