Departamento de Química Inorgánica, Universidad de Santiago de Compostela, E-15782 Santiago de Compostela, Spain.
Dalton Trans. 2013 Jul 28;42(28):10221-32. doi: 10.1039/c3dt32611j.
The reactivity of the unusual d(8) trigonal-bipyramidal systems [MX(PP3)]X (X = Cl: M = Pd(1a), Pt(2a); X = Br: M = Pd(3a), Pt(4a); X = I: M = Pd(5a), Pt(6a); PP3 = tris[2-(diphenylphosphino)ethyl]phosphine) in CHCl3-CH3OH, the square-pyramidal compounds [MCl(NP3)]Cl (M = Pd(7a); Pt(8a); NP3 = tris[2-(diphenylphosphino)ethyl]amine) in CD3OD-DMF and the distorted square-planar mononuclear [MX(PNP)]X (M = Pd: X = Cl(10a); M = Pt: X = I(10b); PNP = bis[2-(diphenylphosphino)ethyl]amine) and the heteronuclear [PdAu2X4(PP3)] [X = I(9a), Cl(14a), Br(15a)] and [MAuX2(PP3)]X [M = Pd: X = Cl(16a); M = Pt: X = Cl(17a), Br(18a)] species in CDCl3 with PPh3 + SnX2 has been explored to establish the factors that influence the nature of the products. With the mononuclear precursors the course of the reaction is strongly dependent on the tripodal or linear arrangement of the polydentate ligand and in the former case on the halogen. Thus, while for chlorides (1a-2a, 7a-8a) and bromides (3a-4a) the reaction led to the trigonal-bipyramidal compounds [M(SnCl3)(AP3)][SnCl3] [A = P: M = Pd(1), Pt(2); A = N: M = Pd(7), Pt(8)], [MBr(PP3)][SnBr3] [M = Pd(4), Pt(6)] containing M-Sn and M-Br bonds, respectively, for iodides (5a-6a) resulted in the unknown neutral square-planar compounds [MI2(PP(PO)2)(SnI2)2] [M = Pd(9) and Pt(10)] bearing two dangling P=O-SnI2 units and P2MI2 environments. However, complexes of the type [PtCl(PP2PO)X]X' [X = SnCl2, X' = SnCl3(11)] and [M(PP(PO)2)2X4]X'2 [X = SnCl2, X' = SnCl3: M = Pd(12), Pt(13)] showing P=O-SnCl2 arms were obtained by direct reaction of [PtCl(PP2PO)]Cl (11a) and [M(PP(PO)2)2]Cl2 [M = Pd(12a), Pt(13a)] with SnCl2 in CH3OH. Although complex 9 was also prepared by interaction of the heteronuclear iodide 9a with PPh3 + SnI2 in CDCl3, the use of the neutral and ionic heteronuclear chlorides and bromides (14a-18a) as starting materials afforded the distorted square-planar ionic systems [MAuX'(PP3)(PPh3)][SnX3]2 [M = Pd: X = Cl, X' = SnCl3(-)(14); X = Br, X' = SnBr3(-)(15); M = Pt: X = Cl, X' = SnCl3(-)(17); X = Br, X' = SnBr3(-)(18)] containing M-SnX3 and P-Au-PPh3 functionalities. It was found that these reactions where the heteronuclear species are the precursors proceed via the trigonal-bipyramidal halides not only with X = Cl and Br(1a-4a) but also I(5a). When the precursors were 10a and 10b the reaction occurred with formation of [Pd(PNP)(PPh3)][SnCl3]2 (23) and [Pt(PNP)(PPh3)][SnCl2I]2 (24) showing M-PPh3 units and trihalostannato counter anions.
在 CHCl3-CH3OH 中，[MX(PP3)]X（X = Cl：M = Pd(1a)，Pt(2a)；X = Br：M = Pd(3a)，Pt(4a)；X = I：M = Pd(5a)，Pt(6a)；PP3 = 三[2-(二苯基膦基)乙基]膦）、[MCl(NP3)]Cl（M = Pd(7a)；Pt(8a)；NP3 = 三[2-(二苯基膦基)乙基]胺）在 CD3OD-DMF 中和畸变的单核[MX(PNP)]X（M = Pd：X = Cl(10a)；M = Pt：X = I(10b)；PNP = 双[2-(二苯基膦基)乙基]胺）和异核[PdAu2X4(PP3)] [X = I(9a)，Cl(14a)，Br(15a)]和[MAuX2(PP3)]X [M = Pd：X = Cl(16a)；M = Pt：X = Cl(17a)，Br(18a)]物种在 CDCl3 中与 PPh3 + SnX2 反应，以确定影响产物性质的因素。对于单核前体，反应的过程强烈依赖于多齿配体的三角锥或线性排列，在前一种情况下还依赖于卤素。因此，对于氯化物（1a-2a、7a-8a）和溴化物（3a-4a），反应导致形成三角双锥化合物[M(SnCl3)(AP3)][SnCl3] [A = P：M = Pd(1)，Pt(2)；A = N：M = Pd(7)，Pt(8)]，[MBr(PP3)][SnBr3] [M = Pd(4)，Pt(6)]，分别含有 M-Sn 和 M-Br 键，而对于碘化物（5a-6a），则得到未知的中性正方形平面化合物[MI2(PP(PO)2)(SnI2)2] [M = Pd(9) 和 Pt(10)]，其中含有两个悬空的 P=O-SnI2 单元和 P2MI2 环境。然而，通过直接反应[PtCl(PP2PO)X]X'[X = SnCl2，X' = SnCl3（11）]和[M(PP(PO)2)2X4]X'2 [X = SnCl2，X' = SnCl3：M = Pd(12)，Pt(13)]得到了类型为[PtCl(PP2PO)X]X'的配合物[PtCl(PP2PO)X]X'，其中 X' = SnCl3，显示出 P=O-SnCl2 臂。尽管 9 也可以通过异核碘化物 9a 与 PPh3 + SnI2 在 CDCl3 中的相互作用来制备，但使用中性和离子异核氯化物和溴化物（14a-18a）作为起始材料，可以得到畸变的正方形平面离子体系[MAuX'(PP3)(PPh3)][SnX3]2 [M = Pd：X = Cl，X' = SnCl3(-)(14)；X = Br，X' = SnBr3(-)(15)；M = Pt：X = Cl，X' = SnCl3(-)(17)；X = Br，X' = SnBr3(-)(18)]，其中含有 M-SnX3 和 P-Au-PPh3 官能团。结果发现，这些反应中异核物种是前体，不仅通过 X = Cl 和 Br(1a-4a)，而且通过 I(5a)进行反应。当前体为 10a 和 10b 时，反应发生形成[Pd(PNP)(PPh3)][SnCl3]2（23）和[Pt(PNP)(PPh3)][SnCl2I]2（24），显示出 M-PPh3 单元和三卤代锡酸根阴离子。
