{dichlorotetrakis(2,6-dimethylphenyl isocyanide)diplatinum} | 110900-14-6

• 英文名称: {dichlorotetrakis(2,6-dimethylphenyl isocyanide)diplatinum}
• CAS: 110900-14-6
• 化学式: C₃₆H₃₆Cl₂N₄Pt₂
• 分子量: 985.775
• InChiKey: JXFMNCKROOFCMI-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  ammonium hexafluorophosphate 、 {dichlorotetrakis(2,6-dimethylphenyl isocyanide)diplatinum} 、 顺-1,2-双(二苯基膦)乙烯 生成 [(cis-1,2-bis(diphenylphosphino)ethene)2(2,6-dimethylphenyl isocyanide)2(platinum(I))2](PF6)2*2dichloromethane
  参考文献：
  名称：

  含螯合二膦的异氰酸铂簇的电化学制备。前所未有的三核铂络合物，其中包括配位不饱和金属中心，[{Pt（diphosphine）（isocyanide）} 2Pt]（PF6）2

  摘要：

  A controlled-potential electrolysis was performed on mononuclear platinum(II) complexes containing aromatic isocyanide (RNC) and diphosphine (diphos) ligands, [Pt(diphos)((RNC)2](PF6)2 diphos = cis-1,2-bis(diphenylphosphino)ethene (dppen) (1), 1,2-bis(diphenylphosphino)ethane (dppe) (2),1,3-bis(diphenylphosphino)propane (dppp) (3),1,4-bis(diphenylphosphino)butane (dppb) (4), and 1,2-bis(di-tert-butylphosphino)ethane (dtbpe) (5); R = 2,6-dimethylphenyl or 2,4,6-trimethylphenyl), which were derived from the reaction of PtCl2(COD) with diphos, RNC, and NH4PF6. Electrolyses of complexes 1-4 at a mercury-pool electrode consumed 1 F mol-1 in acetonitrile at -1.45 to -1.5 V (vs Cp2Fe/CP2Fe+), which gave dinuclear platinum(I) complexes, [Pt4(diphos)2(RNC)2] (PF6)2 (diphos = dppen (6), dppe (7), dppp (8), and dppb (9)). The compounds were characterized by IR, electronic, and H-1 and P-31{H-1} NMR spectroscopy and X-ray crystallographic and EXAFS (extended X-ray absorption fine structure) analyses. Complex 8b (R = 2,4,6-Me3C6H2, diphos = dppp) crystallizes in the monoclinic system, space group P2(1)/c, with a = 14.941(4) angstrom, b = 19.268(6) angstrom, c = 26.002(9) angstrom, beta = 101.23(2)degrees, and Z = 4 (R = 0.059 and R(w) = 0.051 for 5704 independent reflections with I > 3sigma(I)). Complex 8b consists of two platinum atoms, each coordinated by one isocyanide, one diphosphine as a chelating ligand, and the neighboring platinum atom in a square planar array. The length of the Pt-Pt bond is 2.653(1) angstrom. EXAFS analyses showed that the Pt-Pt bond lengths of 6-9 fall within the narrow range of 2.625-2.653 angstrom. Electrolyses of 1, 3, and 5 consumed 1.5 F mol-1 at ca. -1.8 V, which gave trinuclear platinum complexes, [{Pt(diphos)(RNC)}2Pt](PF6)2 (diphos = dppen (13), dppp (14), and dtbpe (15)). Complex 13a (R = 2,6-Me2C6H3) crystallizes in the monoclinic system, space group P2/n, with a = 14.956(4) angstrom, b = 12.395(2) angstrom, c = 22.923(7) angstrom, beta = 104.35(2)degrees, and Z = 2 (R = 0.048 and R(w) = 0.046 for 2872 independent reflections with I > 3sigma(I)); complex 14a (R = 2,6-Me2C6H3) crystallizes in the monoclinic system, space group P2(1), with a = 15.491(3) angstrom, b = 22.575(5) angstrom, c = 10.883(3) angstrom, beta = 107.48(2)degrees, and Z = 2 (R = 0.056 and R(w) = 0.038 for 3156 independent reflections with I > 3sigma(I)); and complex 15a (R = 2,6-Me2C6H3) crystallizes in the monoclinic system, space group C2/c, with a = 19.489(6) angstrom, b = 15.284(5) angstrom, c = 25.804(6) angstrom, beta = 116.34(2)degrees, and Z = 4 (R = 0.045 and R(w) = 0.033 for 2904 independent reflections with I > 3sigma(II). The three platinum atoms were arranged in a linear array with Pt-Pt bond distances of 2.615(1) angstrom (13a), average 2.640 angstrom (14a), and 2.6409(8) angstrom (15a). The outer Pt atoms are coordinated by one isocyanide and one chelating diphosphine, and the central Pt atom is bound only to the two neighboring Pt atoms, resulting in a coordinatively unsaturated platinum center. The coordinatively unsaturated triplatinum complexes 13-15 have 40 valence electrons and are extremely electron-deficient. In the electrolysis of 5a, further reduction led to the formation of a mononuclear hydride complex of platinum, [PtH(dtbpe)-(2,6-Me2C6H3NC)]PF6 (16a). The potentiostatic electrolysis of 2 consumed 1.5 F mol-1 to afford the coordinatively saturated triplatinum complex, [{Pt(dppe)(RNC)}2Pt(RNC)2](PF6)2 (10), instead of the unsaturated trimer. The analogous compounds [{Pt(diphos)(RNC)}2Pt(RNC)2](PF6)2 (diphos = dppen (11) and dtbpe (12)) were also obtained from the reaction of [Pt3-(RNC)8]2+ with diphosphines. Complex 11a (R = 2,6-Me2C6H3) crystallizes in the monoclinic system, space group P2(1)/c, with a = 13.403(3) angstrom, b = 16.126(4) angstrom, c = 21.944(8) angstrom, beta = 98.57(2)degrees, and Z = 2 (R = 0.054 and R(w) = 0.040 for 3064 independent reflections with I > 3 sigma(I)). The Pt-Pt bond length of 2.655(1) angstrom is longer by 0.040 angstrom than that of 13a. A two-electron reduction of 4 at ca. -1.8 V yielded a Hg-Pt mixed-metal cluster, [HgPt6(dppb)2(RNC)8] (17). The length of methylene chain in the diphosphine ligands dramatically influences the structure of the metal-metal bonded platinum clusters. Extended Huckel MO calculations were carried out on the models, [{Pt(PH3)2(HNC)}2Pt]2+ and [{Pt(PH3)2(HNC)}2Pt(HNC)2]2+, for the coordinatively unsaturated and saturated trimers.

  DOI：

  10.1021/om00016a045
• 作为产物：
  描述：

  HgPt6(2,6-xylyl isocyanide)12 、 cis-[PtCl₂(CNXyl)₂] 以 二氯甲烷 为溶剂， 以88%的产率得到{dichlorotetrakis(2,6-dimethylphenyl isocyanide)diplatinum}
  参考文献：
  名称：

  Yamamoto, Yasuhiro; Takahashi, Katsuo; Matsuda, Kiyoshi, Journal of the Chemical Society, Dalton Transactions, 1987, p. 1833 - 1838

  摘要：

  DOI：

文献信息

• Synthesis and characterisation of penta- and hexa-platinum cluster compounds
  作者：Jane L. Haggitt、D. Michael P. Mingos

  DOI：10.1039/dt9940001013

  日期：——

  The reactions of the pentaplatinum cluster compounds [Pt5(mu-SO2)x(mu-CNC8H9)3-x(CNC8H9)7] (x = 0, 2 or 3) with SO2 and CNC8H, (CNC8H9 = 2,6-dimethylphenyl isocyanide) have been studied. The cluster compound [Pt5(mu-CNC8H9)3(CNC8H9)7] 1 was initially synthesised from the reduction of [Pt(CNC8H9)2Cl2] with cobaltocene. It reacts with SO2 to give [Pt5(mu-SO2)3(CNC8H9)7] 2. The reaction of CNC8H9 with 2 results in the formation of [Pt5(mu-SO2)2(mu-CNC8H9)(CNC8H9)7] 3. The structures of 2 and 3 have been solved using single-crystal X-ray crystallography and both are based on an edge-bridged tetrahedral metal core. They are unusual, both containing only three bridging and seven terminal ligands. In the reaction of 1 with SO2 a small amount of [Pt6(mu-SO2)3(CNC8H9)9] was isolated. This compound was characterised on the basis of IR, H-1 NMR spectroscopy and fast atom bombardment mass spectrometry. The metal framework geometry is thought to be related to an edge-bridged trigonal bipyramid.