The reaction of electron rich [PtMe₂(NN)] with SnMe₂Cl₂ in a 1:3/Pt:Sn mole ratio resulted in formation of Pt(IV) complexes [PtMe₂(SnMe₂Cl)Cl(NN)] {NN = 4,4′-Me₂bpy (4,4′-dimethyl-2,2′-bipyridine) (7); 5,5′-Me₂bpy (5,5′-dimethyl-2,2′-bipyridine) (8); bphen (4,7-diphenyl-1,10-phenanthroline) (9)}. NMR data show that the resulting complexes exist as the sole product corresponding to that of trans oxidative addition of SnMe₂Cl₂. The yellow polymorph of complex [PtCl₂(5,5′-Me₂bpy)] (10) was characterized by X-ray crystallography from the reaction of [PtMe₂(5,5′-Me₂bpy)] and excess of SnMe₂Cl₂ due to the reductive elimination of 8. On the other hand, the reaction of [PtMe₂(NN)] with SnEt₂Cl₂ in a 1:3/Pt:Sn mole ratio resulted in formation of new complexes [PtMe₂(SnEt₂Cl)Cl(4,4′-Me₂bpy)] (11), [PtMe₂(SnEt₂Cl)Cl(5,5′-Me₂bpy)].SnEt₂Cl₂ (12) and [PtMe₂(SnEt₂Cl)Cl(bu₂bpy)].SnEt₂Cl₂ (bu₂bpy = 4,4′-di-tert-butyl-2,2′-dipyridine) (13). NMR data indicate that the PtSnEt₂Cl bond is weaker than the PtSnMe₂Cl bond. The X-ray crystal structure of 13 reveals that organoplatinum(IV) complex acts as a donor to the SnEt₂Cl₂ to form an adduct in a distorted trigonal bipyramid with the axial Cl⋯SnCl and equatorial SnEt₂Cl units. Moreover, the X-ray crystal structure of the new yellow form of [PtClMe(4,4′-Me₂bpy)] (14), which has been formed by the crystallization of a mixture of [PtMe₂(4,4′-Me₂bpy)] and excess of SnEt₂Cl₂, is described. The reaction of dimethylplatinum(II) complexes with dimethyltin diisothiocanate are reported for the first time which occur via Sn-NCS bond cleavage to afford the organoplatinum(IV) complexes [PtMe₂(SnMe₂NCS)(SCN)(NN)] {NN = bpy (17); phen (18); 5,5′-Me₂bpy (19); bu₂bpy (20); bphen (21)}. The crystal structures of the novel thiocyanatoplatinum(IV) complexes [PtMe₂(SCN)₂(bpy)] (22) and [PtMe₂(SCN)₂(5,5′-Me₂bpy)]. H₂O (23) are discussed which have been obtained due to the α-elimination of SnMe₂. The crystal structures of 22–23 show that platinum adopts a slightly distorted octahedral geometry with trans- Pt(SCN)₂ configuration in which SCN is bonded through sulfur atom while the nitrogen atom is coordinated to tin. NMR data indicate that the products dissociate via α-elimination of SnMe₂ or reductive elimination of organotin(IV) compound and the stability of the organoplatinum(IV) compounds varies according to the trends [PtMe₂(SnMe₂Cl)Cl(NN)]>[PtMe₂(SnMe₂NCS)(SCN)(NN)]>[PtMe₂(SnEt₂Cl)Cl(NN)].

摩尔比为1：3 / Pt：Sn的富电子[PtMe ₂（NN）]与SnMe ₂ Cl ₂的反应导致形成Pt（IV）配合物[PtMe ₂（SnMe ₂ Cl）Cl（NN）] {NN = 4,4'-Me ₂ bpy（4,4'-二甲基-2,2'-联吡啶）（7）；5,5'-Me ₂ bpy（5,5'-二甲基-2,2'-联吡啶）（8）; bphen（4,7-二苯基-1,10-菲咯啉）（9）}。NMR数据表明，所形成的络合物作为唯一产物而存在，其对应于SnMe ₂ Cl ₂的反氧化添加。络合物[PtCl ₂（5,5'-Me通过[PtMe ₂（5,5'-Me ₂ bpy）]与由于还原性消除8而过量的SnMe ₂ Cl ₂的反应，通过X射线晶体学表征了₂ bpy）]（10）。另一方面，[PtMe ₂（NN）]与SnEt ₂ Cl _2的摩尔比为1：3 / Pt：Sn的反应导致形成新的络合物[PtMe ₂（SnEt ₂ Cl）Cl（4,4） ′-Me ₂ bpy）]（11），[PtMe ₂（SnEt ₂ Cl）Cl（5,5'-Me ₂ bpy）]。SnEt ₂ Cl ₂（12）和[PtMe ₂（SnEt ₂ Cl）Cl（bu ₂ bpy）]。SnEt ₂ Cl ₂（bu ₂ bpy = 4,4'-二叔丁基-2,2'-二吡啶）（13）。NMR数据表明，Pt SnEt ₂ Cl键比Pt SnMe ₂ Cl键弱。13的X射线晶体结构表明，有机铂（IV）络合物充当SnEt ₂ Cl ₂的供体，在具有轴向Cl⋯Sn Cl和赤道SnEt ₂的扭曲三角锥中形成加合物。Cl单位。此外，[PtClMe（4,4'-Me ₂ bpy）]（14）的新黄色形式的X射线晶体结构是通过[PtMe ₂（4,4' -Me ₂ bpy）]和过量的SnEt ₂ Cl ₂进行了描述。首次报道了二甲基铂（II）配合物与二异硫代二甲基锡二甲酸酯的反应，这是通过Sn-NCS键裂解产生有机铂（IV）配合物[PtMe ₂（SnMe ₂ NCS）（SCN）（NN）] {NN = bpy（17）; 苯（18）; 5,5'-Me ₂ bpy（19）; 埠₂bpy（20）; bphen（21）}。新型硫氰酸根合铂（IV）配合物[PtMe ₂（SCN）₂（bpy）]（22）和[PtMe ₂（SCN）₂（5,5'-Me ₂ bpy）]的晶体结构。讨论了由于SnMe ₂的α消除而获得的H ₂ O（23）。22 – 23的晶体结构表明，铂具有稍微扭曲的八面体几何结构，并且具有反式-Pt（SCN）₂SCN通过硫原子键合，而氮原子与锡配位的构型。NMR数据表明，产物通过α-消除SnMe ₂或还原性消除有机锡（IV）化合物而解离，有机铂（IV）化合物的稳定性根据趋势而变化[PtMe ₂（SnMe ₂ Cl）Cl（NN） ]> [PtMe ₂（SnMe ₂ NCS）（SCN）（NN）]> [PtMe ₂（SnEt ₂ Cl）Cl（NN）]。