[Pt2PdCl6(1,2-bis(diphenylphosphino)acetylene)2] | 189934-12-1

• 英文名称: [Pt2PdCl6(1,2-bis(diphenylphosphino)acetylene)2]
• CAS: 189934-12-1
• 化学式: C₅₂H₄₀Cl₆P₄PdPt₂
• 分子量: 1498.08
• InChiKey: WSLGGKFJTNZNRM-UHFFFAOYSA-H

反应信息

• 作为产物：
  描述：

  [Pt2Cl4(1,2-bis(diphenylphosphino)acetylene)2] 、 palladium dichloride 以 N,N-二甲基甲酰胺 为溶剂， 以53%的产率得到[Pt2PdCl6(1,2-bis(diphenylphosphino)acetylene)2]
  参考文献：
  名称：

  Binuclear palladium(II), platinum(II) and platinum(IV) complexes containing 1,2-bis (diphenylphosphino)acetylene: different orientations of the diphosphine-bridges due to metal-phosphorus dπ-dπ back bonding

  摘要：

  Several novel Pd(II), Pt(II) and Pt(IV) dimers containing 1,2-bis(diphenylphosphino)acetylene (dppa) as bridging ligand have been prepared and characterized by X-ray diffraction methods, NMR spectroscopy (Pt-195{H-1}, P-31{H-1}, IR spectroscopy, elemental analyses and melting points. The X-ray structures of the former reported complexes [Pd2Cl4(dppa)(2)] (1) and [Pt2Cl4(dppa)(2)] (2) are given for the first time: 1: monoclinic, P2(1)/n, a=14.401(3), b=12.100(2), c=15.880(3) Angstrom, beta=91.36(3)degrees, Z=2, R=0.039 for 6432 observed reflections (I>3 sigma(I)); 2: orthorhombic, Pbcn, a=13.995(3), b=17.669(4), c=21.960(4) Angstrom, Z=4, R=0.052 for 2332 observed reflections (I>3 sigma(I)). These two X-ray structures are discussed with respect to the farmer given ambiguous interpretation of the X-ray structure of [PtPdCl4(dppa)(2)]. Replacement of the chlorides in 1 or 2 by iodides leads to [Pd2I4(dppa)(2)] (3) or [Pt2I4(dppa)(2)] (4). 4 is also fully characterized by an X-ray structure analysis for the first time: 4: monoclinic, P2(1)/c, a=10.586(2), b=30.526(6), c=18.383(4) Angstrom, beta=100.09(3)degrees, Z=4, R=0.061 for 4698 observed reflections (I>3 sigma(I)).The X-ray structures of 1, 2 and 4 reveal different orientations of the dppa bridges due to metal-phosphorus d pi-d pi back bonding leading to different angles between the square-planar coordination units, respectively. Replacement of the chlorides in 1 by NO2- leads to [Pd-2(NO2)(4)(dppa)(2)] (5), whereas in 2 only one chloride can be substituted by NO2- and [Pt2Cl3(NO2)(dppa)(2)] (6) is formed. A similar reaction of 2 with 2,2'-bipyridine (bipy) produces [Pt2Cl2(dppa)(2)(bipy)](BF4)(2) (7). Oxidation of 2 by chlorine gives the Pt(IV) dimer [Pt2Cl8(dppa)(2)] (8). An equimolar amount of PdCl2 reacts with one triple bond of 2 leading to [Pt2PdCl6(dppa)(2)] (9). In an analogous manner [Pd4Cl8(dppa)(2)] (10) is formed from 1 and two equimolar amounts of PdCl2. The stability and reactivity of complexes 1-10 are discussed with respect to the X-ray structures of 1, 2, 4 and [PtPdCl4(dppa)(2)].

  DOI：

  10.1016/s0020-1693(96)05449-7