trans-hydridoiodobis(tricyclohexylphosphine)platinum(II) | 60159-01-5

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: trans-hydridoiodobis(tricyclohexylphosphine)platinum(II)
• 英文别名: trans-hydridoiodobis(tricyclohexylphosphine)platinum；trans-(P(cyclohexyl)3)2Pt(H)(I)；trans-[PtHI(PCy₃)₂]
• CAS: 60159-01-5
• 化学式: C₃₆H₆₇IP₂Pt
• 分子量: 883.86
• InChiKey: OILAGGYMVJJXQZ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  13.55
• 重原子数：
  40.0
• 可旋转键数：
  8.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  Brookhart's acid 、 trans-hydridoiodobis(tricyclohexylphosphine)platinum(II) 以 二氯甲烷-D2 为溶剂， 生成 bis(tricyclohexyl-l5-phosphaneyl)platinum(VI) dihydride diiodide 、 [((P(cyclohexyl)3)2Pt(H))2I][B(3,5-C6H3(CF3)2)4]
  参考文献：
  名称：

  Stahl, Shannon S.; Labinger, Jay A.; Bercaw, John E., Inorganic Chemistry, 1998, vol. 37, # 10, p. 2422 - 2431

  摘要：

  DOI：
• 作为产物：
  描述：

  trans-hydridoamminebis(tricyclohexylphosphine)platinum perchlorate 在 NaNH₂ 、 methyl iodide 作用下， 以 氘代苯 、 氨 为溶剂， 生成 trans-hydridoiodobis(tricyclohexylphosphine)platinum(II)
  参考文献：
  名称：

  铂（II）单体和二聚酰胺配合物的合成和反应化学

  摘要：

  A series of complexes trans-[PtH(NH3)L2]ClO4 (L = PPh3, PEt3, PCy3), trans-[PtMe(NH3)L2]ClO4 (L = PPh3, PEt3, PMePh2, PCy3), and [PtMe(NH3)dppe]ClO4 have been synthesized from trans-PtH(ClO4)L2, trans-PtMe(ClO4)L2, and PtMe(ClO4)dppe and ammonia, respectively. Reacting trans-[PtH(NH3)L2]ClO4 (L = PPh3, PEt3) with NaNH2 gives [PtH(mu-NH2)L]2 as a mixture of anti and syn isomers. The complexes reductively eliminate ammonia. Reacting trans-[PtMe(NH3)L2]ClO4 (L = PPH3, PEt3, PMePh2) with NaNH2 gives the stable complexes [PtMe(mu-NH2)L]2 as mixtures of anti and syn isomers. For L = PPh3, PMePh2, PEt3, the percentage anti isomer is 100, 75, and 50, respectively. For L = PEt3, the intermediate complex trans-PtMe(NH2)(PEt3)2 has been observed. Reacting [PtMe(mu-NH2)L]2 with L (L = PPh3, PEt3) gives cis-PtMe(NH2)L2. Reacting trans-[PtH(NH3)(PCy3)2]ClO4, trans-[PtMe(NH3)(PCy3)2]ClO4, or trans-[PtPh(NH3)(PCy3)2]ClO4 with NaNH2 gives trans-PtH(NH2)(PCy3)2, trans-PtMe(NH2)(PCy3)2, or trans-PtPh(NH2)(PCy3)2. Reacting [PtMe(mu-Cl)PCy3]2 with AgClO4 then NH3 gives [PtMe(NH3)2PCy3]ClO4. Treating [PtMe(NH3)2PCy3] with NaNH2 gives an equimolar mixutre of anti and syn isomers of [PtMe(mu-NH2)PCy3]2. The syn isomer, which has been isolated, converts to a mixture of syn and anti in the presence of tricyclohexylphosphine in CDCl3 solution. The compound anti-[PtMe(mu-NH2)PPh3]2 crystallizes in the space group C2/c with a = 22.592 (5) angstrom, b = 11.844 (3) angstrom, c = 29.403 (6) angstrom, beta = 116.43 (2) degrees, and Z = 8. The two crystallographically independent molecules with Pt(1)-Pt(1A) and Pt(2)-Pt(2A) distances of 3.106 (1) and 3.117 (1) angstrom, respectively, are associated by Pt...H interactions. The complex trans-PtMe(NH2)(PCy3)2 reacts with CF3SO3H to give trans-[PtMe(NH3)(PCy3)2]CF3SO3. The complex trans-PtPh(NH2)(PCy3)2 reacts with CF3SO3H and H2O to give trans-[PtPh(NH3)(PCy3)2]CF3SO3 and trans-PtPh(NH2)(PCy3)2 reacts with methyl iodide and allyl chloride to give trans-PtPhI(PCy3)2 and trans-PtPhCl(PCy3)2, respectively. Carbon dioxide reacts with trans-PtPh(NH2)(PCy3)2 to give trans-PtPh(NHCO2H)(PCy3)2 then trans-PtPh(OCONH2)(PCy3)2.

  DOI：

  10.1021/om00049a020

文献信息

• Platinum–phosphorus bond lengths and nuclear magnetic resonance coupling constants in complexes of tri(n-alkyl)- and tricyclohexylphosphines. Crystal and molecular structure of trans-di-iodobis(trimethylphosphine)platinum(<scp>II</scp>)
  作者：Peter B. Hitchcock、Barbara Jacobson、Alan Pidcock

  DOI：10.1039/dt9770002038

  日期：——

  atoms and the Iodide ligands, with consequent lengthening of the Pt–P and Pt–I bonds in trans-[PtI2P(C6H11)3}2]. The coupling constants 1J(Pt–P) for trans-di-iodo(tricyclohexylphosphine) complexes are larger than expected, probably due to large |ΨPt,6s(0)|2/(3ΔE) terms for complexes with bonds lengthened by steric repulsions.

  已经确定了反式-[ Ptl 2（PMe 3）2 ]的晶体和分子结构。晶体是单斜晶系，空间群P 2 1 / Ñ，具有一个= 8.845（6），b = 10.298（8），C ^ = 7.936（5），β= 95.12（4）°，并ž = 2强度有用衍射仪测量，并通过重原子法解析结构，并精炼至R 0.041。晶体包含离散的中心对称分子，与方形平面配位只有很小的偏差[Pt–P 2.315（4）和Pt–I 2.599（2）Å]。分子内H⋯I距离比in反式-[PtI 2 P（C 6 H 11）3 } 2 ]。P（C 6 H 11）3配体的环己基构型由H⋯H相互作用决定，并导致两个α-碳原子上的氢原子与碘化物配体之间发生强H⋯I相互作用，因此加长了反式-[PtI 2 P（C 6 H 11）3 } 2 ]中的Pt–P和Pt–I键。反式的耦合常数1 J（Pt–P）-二-碘（三环己基膦）络合物比预期的大，可能是由于|
• Transition-Metal π-Ligation of a Tetrahalodiborane
  作者：Holger Braunschweig、Rian D. Dewhurst、J. Oscar C. Jiménez-Halla、Eduard Matito、Jonas H. Muessig

  DOI：10.1002/anie.201709515

  日期：2018.1.8

  of tetraiododiborane (B2I4) with trans‐[Pt(BI2)I(PCy3)2] gives rise to the diplatinum(II) complex [(Cy3P)(I2B)Pt}2(μ2:η3:η3‐B2I4)], which is supported by a bridging diboranyl dianion ligand [B2I4]2−. This complex is the first transition‐metal complex of a diboranyl dianion, as well as the first example of intact coordination of a B2X4 (X=halide) unit of any type to a metal center.

  四碘二硼烷（B 2 I 4）与反式-[Pt（BI 2）I（PCy 3）2 ]的反应生成二铂（II）络合物[（Cy 3 P）（I 2 B）Pt} 2（μ 2：η 3：η 3 -B 2我4）]，其通过桥连二价阴离子乙硼配位体[B支持2我4 ] 2-。该络合物是二硼烷基二价阴离子的第一个过渡金属络合物，也是B 2 X 4完整配位的第一个实例。 金属中心的任何类型的（X =卤化物）单元。