The complex [PtMe2(dppa)], 1a, dppa = Ph2PNHPPh2, which has previously been prepared as a mixture with the dimeric form [Pt2Me4(µ-dppa)2], was synthesized in pure form by the reaction of [PtCl2(dppa)] with MeLi. The aryl analogue [Pt(p-MeC6H4)2(dppa)], 1b, was prepared by replacement of SMe2 in cis-[Pt(p-MeC6H4)2(SMe2)2] with dppa. The reaction of the chelate complexes 1 with one equiv. of dppa afforded the complexes [PtR2(dppa-P)2], RMe, 2a and R = p-MeC6H42b. The reaction of [PtR2(dppa)], 1, with neat MeI gave the organoplatinum(IV) complexes [PtR2MeI(dppa)], RMe, 5a and R = p-MeC6H4, 5b. The structure of 5a, determined by X-ray crystallography, indicated that the complex undergoes self-assembly by intermolecular NâHâ¯IâPt hydrogen bonding. MeI was also double oxidatively added to organodiplatinum(II) complex cis,cis-[Me2Pt(µ-SMe2)(µ-dppa)PtMe2], to give diorganoplatinum(IV) complex [Me3Pt(µ-dppa)(µ-I)2PtMe3], 4. The aryl analogue organodiplatinum(II) complex cis,cis-[(p-MeC6H4)2Pt(µ-SMe2)(µ-dppa)Pt(p-MeC6H4)2], 3b, was prepared by the reaction of cis-[Pt(p-MeC6H4)2(SMe2)2] with half equiv. of dppa, but 3b refused to react with MeI, probably because of the steric effects of the aryl ligands. The tetramethyl complex [PtMe4(dppa)], 6, was prepared either by reaction of 5a with MeLi or by replacement of SMe2 in [Pt2Me8(µ-SMe2)2] with dppa. All the complexes were fully characterized in solution by multinuclear NMR (1H, 13C, 31P and 195Pt) methods and their coordination compared with that of the corresponding known dppm complexes.
通过[PtCl2(dppa)]与 MeLi 的反应,合成了纯态的[PtMe2(dppa)]复合物 1a(dppa = Ph2
PNHPPh2),该复合物以前曾作为与二聚态[Pt2Me4(µ-dppa)2]的混合物制备。芳基类似物[Pt(p-MeC6H4)2(dppa)]1b 是用 dppa 取代顺式[Pt(p-MeC6H4)2(SMe2)2]中的 SMe2 而制备的。螯合物 1 与一当量的 dppa 反应得到[PtR2(dppa-P)2],RMe,2a 和 R = p-MeC6H42b。将[PtR2(dppa)]1 与纯 MeI 反应,可得到有机
铂(IV)络合物[PtR2MeI(dppa)],RMe,5a 和 R = p-MeC6H4,5b。通过 X 射线晶体学测定的 5a 的结构表明,该配合物通过分子间 NâHâ¯IâPt 氢键进行自组装。在有机
铂(II)复合物顺式、顺式-[Me2Pt(µ-SMe2)(µ-dppa)PtMe2]中加入 MeI,也可得到二
铂(IV)复合物[Me3Pt(µ-dppa)(µ-I)2PtMe3],即 4。顺式-[(p-MeC6H4)2Pt(µ-SMe2)(µ-dppa)Pt(p-MeC6H4)2]与半当量 dppa 反应制备出芳基类似物有机
铂(II)络合物顺式-[(p-MeC6H4)2Pt(µ-SMe2)(µ-dppa)Pt(p-MeC6H4)2]3b,但 3b 拒绝与 MeI 反应,可能是因为芳基
配体的立体效应。通过 5a 与 MeLi 反应或用 dppa 取代 [Pt2Me8(µ-SMe2)2]中的 SMe2,制备出了四甲基配合物 [PtMe4(dppa)],即 6。通过多核核磁共振(1H、13C、31P 和 195Pt)方法对所有配合物在溶液中的性质进行了全面鉴定,并将它们的配位与相应的已知 dppm 配合物的配位进行了比较。