Hoseini S Jafar, Mohamadikish Maryam, Kamali Katayon, Heinemann Frank W, Rashidi Mehdi
Department of Chemistry, Faculty of Sciences, Shiraz University, Shiraz, 71454, Iran.
Dalton Trans. 2007 May 7(17):1697-704. doi: 10.1039/b700009j. Epub 2007 Mar 15.
The complex [PtMe(2)(dppa)], 1a, dppa = Ph(2)PNHPPh(2), which has previously been prepared as a mixture with the dimeric form [Pt(2)Me(4)(micro-dppa)(2)], was synthesized in pure form by the reaction of [PtCl(2)(dppa)] with MeLi. The aryl analogue [Pt(p-MeC(6)H(4))(2)(dppa)], 1b, was prepared by replacement of SMe(2) in cis-[Pt(p-MeC(6)H(4))(2)(SMe(2))(2)] with dppa. The reaction of the chelate complexes 1 with one equiv. of dppa afforded the complexes [PtR(2)(dppa-P)(2)], R=Me, 2a and R=p-MeC(6)H(4) 2b. The reaction of [PtR(2)(dppa)], 1, with neat MeI gave the organoplatinum(iv) complexes [PtR(2)MeI(dppa)], R=Me, 5a and R=p-MeC(6)H(4), 5b. The structure of 5a, determined by X-ray crystallography, indicated that the complex undergoes self-assembly by intermolecular N-H . . . I-Pt hydrogen bonding. MeI was also double oxidatively added to organodiplatinum(ii) complex cis,cis-[Me(2)Pt(micro-SMe(2))(micro-dppa)PtMe(2)], to give diorganoplatinum(iv) complex [Me(3)Pt(micro-dppa)(micro-I)(2)PtMe(3)], 4. The aryl analogue organodiplatinum(ii) complex cis,cis-[(p-MeC(6)H(4))(2)Pt(micro-SMe(2))(micro-dppa)Pt(p-MeC(6)H(4))(2)], 3b, was prepared by the reaction of cis-[Pt(p-MeC(6)H(4))(2)(SMe(2))(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 [PtMe(4)(dppa)], 6, was prepared either by reaction of 5a with MeLi or by replacement of SMe(2) in [Pt(2)Me(8)(micro-SMe(2))(2)] with dppa. All the complexes were fully characterized in solution by multinuclear NMR ((1)H, (13)C, (31)P and (195)Pt) methods and their coordination compared with that of the corresponding known dppm complexes.
配合物[PtMe₂(dppa)]（1a，dppa = Ph₂PNHPPh₂）先前是以与二聚体形式[Pt₂Me₄(μ - dppa)₂]的混合物形式制备的，通过[PtCl₂(dppa)]与MeLi反应以纯形式合成。芳基类似物[Pt(p - MeC₆H₄)₂(dppa)]（1b）是通过用dppa取代顺式[Pt(p - MeC₆H₄)₂(SMe₂)₂]中的SMe₂制备的。螯合配合物1与一当量的dppa反应得到配合物[PtR₂(dppa - P)₂]，R = Me（2a）和R = p - MeC₆H₄（2b）。[PtR₂(dppa)]（1）与纯MeI反应得到有机铂（IV）配合物[PtR₂MeI(dppa)]，R = Me（5a）和R = p - MeC₆H₄（5b）。通过X射线晶体学确定的5a的结构表明该配合物通过分子间N - H...I - Pt氢键进行自组装。MeI也被双氧化加成到有机二铂（II）配合物顺式，顺式 - [Me₂Pt(μ - SMe₂)(μ - dppa)PtMe₂]上，得到二有机铂（IV）配合物[Me₃Pt(μ - dppa)(μ - I)₂PtMe₃]（4）。芳基类似物有机二铂（II）配合物顺式，顺式 - [(p - MeC₆H₄)₂Pt(μ - SMe₂)(μ - dppa)Pt(p - MeC₆H₄)₂]（3b）是通过顺式[Pt(p - MeC₆H₄)₂(SMe₂)₂]与半当量的dppa反应制备的，但3b拒绝与MeI反应，可能是由于芳基配体的空间效应。四甲基配合物[PtMe₄(dppa)]（6）可通过5a与MeLi反应或用dppa取代[Pt₂Me₈(μ - SMe₂)₂]中的SMe₂制备。所有配合物在溶液中通过多核NMR（¹H、¹³C、³¹P和¹⁹⁵Pt）方法进行了全面表征，并将它们的配位情况与相应已知的dppm配合物进行了比较。
