3,3-bis(dimethylphenylphosphine)-1,2-diarsa-3-palladium-closo-dodecaborane | 138826-99-0

• 英文名称: 3,3-bis(dimethylphenylphosphine)-1,2-diarsa-3-palladium-closo-dodecaborane
• CAS: 138826-99-0
• 化学式: C₁₆H₃₁As₂B₉P₂Pd
• 分子量: 638.932
• InChiKey: QBQAVOJXSVWAON-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 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：

  cis-[PdCl₂(CN(t-Bu))₂] 、 3,3-bis(dimethylphenylphosphine)-1,2-diarsa-3-palladium-closo-dodecaborane 以 四氢呋喃 为溶剂， 以28.3%的产率得到1-(t)BuNC-5-CN-1-(PMe2Ph)-closo-1,2,3-PdAs2B9H8
  参考文献：
  名称：

  Palladium-Assisted Cyano Substitution Reactions of (PMe2Ph)2Pd(B9H9As2) and (PMe2Ph)2Pd(B9C2H11). X-ray Crystal and Molecular Structures of 5-CN-1,1-(PMe2Ph)2-closo-1,2,3-PdAs2B9H8, 1-tBuNC-5-CN-1-(PMe2Ph)-closo-1,2,3-PdAs2B9H8, and 4,5-(CN)2-1,1-(PMe2Ph)2-closo-1,2,3-PdC2B9H9

  摘要：

  The reaction of 1,1-(PMe(2)Ph)(2)-closo-1,2,3-PdAs2B9H9 (A) with (1)BuNC formed low yields of 5-CN-1,1-(PMe(2)-Ph)(2)-closo-1,2,3-PdAs2B9K8 (2) and/or 1-(t)BuNC-5-CN-1-(PMe(2)Ph)-closo-1,2,3-PdAs2B9H8 (3). The use of ((t)BuNC)(2)PdCl2 as a reagent in this reaction gave an improved yield of compound 3. Similar reaction of 1,1-(PMe(2)Ph)(2)-closo-1,2,3-PdC2B9H11 (4) with ((t)BuNC)(2)PdCl2 gave 4.5-(CN)(2)-1,1-(PMe(2)Ph)(2)-closo-1,2,3-PdC2B9H9 (5). Reaction of A with (PMe(2)Ph)(2)P(CN)(2) gave 1-CN-1,5-(PMe(2)Ph)(2)-closo-1,2,3-PdAs2B9H8 (1) in low yield. Compounds 2, 3, and 5 were characterized by X-ray diffraction studies. Compound 2 consisted of bright purple crystals of monoclinic space group P2(1)/n, with a = 12.460(2) Angstrom, b = 11.583(2) Angstrom, c = 19.114(4) Angstrom, beta = 107.31(1)degrees, and Z = 4. The structure was determined by conventional heavy-atom methods and refined to a final value of R = 0.0432 (3899 reflections) and R(w) = 0.0458. Compound 3 consisted of magenta plates with triclinic space group , with a = 11.586(3) Angstrom, b = 11.813(3) Angstrom, c = 9.799(2) Angstrom, alpha = 95.33(1)degrees, beta = 114.58(1)degrees, gamma = 80.17(1)degrees, and Z = 2. The structure was determined by conventional heavy-atom methods and refined to a final value of R = 0.0235 (3323 reflections), R(w) = 0.0245. Compound 5 consisted of red needles with monoclinic space group P2(1)/n, with a = 10.383(2) Angstrom, b = 18.875(3) Angstrom, c = 13.682(2) Angstrom, beta = 105.41(1)degrees, and Z = 4. The structure was determined by conventional heavy-atom methods and refined to a final value of R = 0.0362 (3547 reflections), R(w) = 0.0335.

  DOI：

  10.1021/ic00130a007
• 作为产物：
  描述：

  ortho-diarsacarborane 、 dichlorobis(dimethylphenylphosphine)palladium(II) 在 piperidine 、 n-butyl lithium 作用下， 以 四氢呋喃 为溶剂， 以57%的产率得到3,3-bis(dimethylphenylphosphine)-1,2-diarsa-3-palladium-closo-dodecaborane
  参考文献：
  名称：

  Jasper Jr., Steve A.; Roach, Steve; Stipp, John N., Inorganic Chemistry, 1993, vol. 32, # 14, p. 3072 - 3080

  摘要：

  DOI：

文献信息

• Metallaheteroborane chemistry. Part 9. Syntheses and spectroscopy of platinum and palladium phosphine complexes containing η⁵-{As₂B₉}-based cluster ligands. Crystal structures of [3,3-L₂-closo-3,1,2-PtAs₂B₉H₉](L = PPh₃or PMe₂Ph) and [3-Cl-3,8-(PPh₃)₂-closo-3,1,2-PdAs₂B₉H₈]
  作者：Marguerite McGrath、Trevor R. Spalding、Xavier L. R. Fontaine、John D. Kennedy、Mark Thornton-Pett

  DOI：10.1039/dt9910003223

  日期：——

  The reaction between [Pt(PPh3)4] and closo-1,2-As2B10H10 in ethanol gives [3,3-(PPh3)2-closo-3,1,2-PtAs2B9H9] 1 in low yield (9%). Reaction of [nido-7,8-As2B9H10]- and [MCl2(PR3)2] in tetrahydrofuran(thf) in the presence of a ten-fold excess of NEt3 affords [3,3-(PR3)2-closo-3,1,2-MAs2B9H9] (M = Pt, R3 = Me2Ph 2; M = Pd, R3 = Ph3 3 or Me2Ph 4) and [3-Cl-3,8-(PR3)2-closo-3,1,2-PdAs2B9H8] (R3 = Ph3 5; or R3 = Me2Ph, 6) in low-to-moderate (20-45%) yields. X-Ray diffraction analyses of 1, 2 and 5 confirm the closo icosahedral MAs2B9 cage structures and the presence of a MAs2 triangulated face in each of these molecules. Both compounds 1 and 2 crystallise in the monoclinic space group P2(1)/n with Z = 4. Cell dimensions: 1, a = 1230.0(2), b = 1736.5(4), c = 1881.0(3) pm and beta = 91.44(2)-degrees; 2, a = 1308.6(3), b = 1058.0(2), c = 1934.7(3) pm and beta = 104.45(2)-degrees. The structure of 1 was refined to a final R of 0.0574 (R' 0.0532) for the 4160 reflections with I greater-than-or-equal-to 2.0-sigma(I). One of the As atoms is disordered over two sites. Calculated Pt-As distances are 259.1(5), 255.7(5) and 264.0(6) pm, As-As 251.5(6) and 243.5(5) pm. Structure 2 had a final R of 0.0384 (R' 0.0376) for the 3778 reflections with I greater-than-or-equal-to 2.0-sigma(I). The Pt-As distances are 265.5(4) and 254.5(4) pm and As-As is 249.7(3) pm. Compound 5 crystallises in the triclinic space group P1BAR with Z = 2, a = 1037.8(2), b = 1321.9(3), c = 1712.9(3) pm, alpha = 103.67(1), beta = 93.19(1) and gamma = 110.86(1)-degrees; final R = 0.0392 (R' = 0.0408) for 4688 reflections with I greater-than-or-equal-to 2.0-sigma(I). The Pd-As distances are 256.3(4) and 253.9(4) pm and As-As is 247.7(3) pm. Compounds 1-6 were characterised by multielement NMR spectroscopy. Variable-temperature H-1 studies of 2, 4 and 6 show the metal to As2B9 ligand bonding is fluxional at room temperature with DELTA-G double-ended dagger 298 < ca. 30 kJ mol-1 for 2 and 4 and possibly slightly higher for 6 at ca. 32 kJ mol-1. An analysis of the frontier molecular orbitals of the model ligand P2B9H9 and their possible interactions with a Pt(PH3)2 group shows no clear preference between the two possible conformations that the PtP2 unit could adopt above the P2B3 face to which it bonds.