Ni (1,2-bis(dicyclohexylphosphanyl)ethane) I2 | 97921-19-2

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: Ni (1,2-bis(dicyclohexylphosphanyl)ethane) I2
• CAS: 97921-19-2
• 化学式: C₂₆H₄₈I₂NiP₂
• 分子量: 735.114
• InChiKey: BVBJTYCLGZNGLB-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  3.29
• 重原子数：
  31.0
• 可旋转键数：
  4.0
• 环数：
  5.0
• 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

• 作为产物：
  描述：

  nickel(II) chloride hexahydrate 、 氢碘酸 、 1,2-双(二环己基磷基)-乙烷 以 甲醇 、 水 为溶剂， 以62%的产率得到Ni (1,2-bis(dicyclohexylphosphanyl)ethane) I2
  参考文献：
  名称：

  New nickel-containing homogeneous hydrogenation catalysts

  摘要：

  The didentate phosphane ligands 1,3-bis(di(ortho-methoxyphenyl)phosphanyl)-2-propanol (o-MeO-dpppol) and 1,2-bis(dicyclohexylphosphanyl)ethane (dcpe) have been used in a study towards catalytic hydrogenation using homogeneous nickel catalysts. The nickel halide complexes [Ni(o-MeO-dpppol)X-2] and [Ni(dcpe)X-2] (X = Cl, Br or I) have been synthesized and were characterized using electronic absorption and IR spectroscopy. The structures of the complexes [Ni(o-MeO-dpppol)Cl-2] and [Ni(dcpe)Cl-2] have been determined by X-ray crystallography. The nickel ions in these complexes are in (distorted) square-planar geometries with NiP2Cl2 chromophores. The synthesized halide complexes and in situ mixtures of nickel acetate and the ligands were tested on catalytic activity in homogeneous hydrogenation. The ligand dcpe yields very active catalysts; turnover numbers up to 3000 in I h have been obtained. Generally, it appeared that the catalytic activities are higher in methanol than in methanol/dichloromethane mixtures. It was found that the catalytic activities observed for complexes containing the ligand o-MeO-dpppol are less reproducible than those of catalysts with the ligand dcpe. This lower reproducibility is probably related to the fact that the former ligand is more readily oxidized. (C) 2003 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s1381-1169(03)00216-4

文献信息

• Bennett, Martin A.; Hambley, Trevor W.; Roberts, Nicholas K., Organometallics, 1985, vol. 4, # 11, p. 1992 - 2000
  作者：Bennett, Martin A.、Hambley, Trevor W.、Roberts, Nicholas K.、Robertson, Glen B.

  DOI：——

  日期：——
• Star porphyrazines: peripheral chelation of porphyrazineoctathiolate by diphosphinonickel ions
  作者：Christopher S. Velazquez、Theodore F. Baumann、Marilyn M. Olmstead、Hakon Hope、Anthony G. M. Barrett、Brian M. Hoffman

  DOI：10.1021/ja00075a016

  日期：1993.11

  We have synthesized new pentametallic macrocyclic complexes based on the polynucleating ligand, porphyrazine-2,3,7,8,12,13,17,18-octathiolate, (pzot)8-. This ligand can be thought of as a porphyrazine (tetraazaporphyrin) bearing four dithiolene moieties peripherally at the beta-pyrrole positions, and we show that a transition-metal ion can be chelated to each of the four peripheral dithiolene moieties. The complexes [(P-P)Ni]4[Ni(pzot)] (2a, P-P = dppe; 2b, P-P = dppy; 2c, P-P = dppb; 2d, P-P = dcpe) have been synthesized and characterized. Complex 2a crystallizes in the orthorhombic space group Cmc2(1) (No. 36) with 4 macrocycles and 16 solvent molecules (N,N-dimethylformamide) in a unit cell of dimensions a = 24.630(5) angstrom, b = 20.607(4) angstrom, c = 30.675(6) angstrom. The [Ni(pzot)]8- ligand in 2a coordinates four Ni(P-P) moieties around its periphery with the two thiolate sulfur atoms of each pyrrole binding a nickel ion in a bidentate (S-S) coordination mode. This is in contrast to the reaction of [Ni(pzot)]8- with SnR2X2, which yielded Ni(pzot)(SnR2)4 (1), where each tin is coordinated in the tridentate (S-N-S) mode, with the thiolate sulfur atoms from two pyrroles and one m-nitrogen atom as ligands from the macrocycle (Velazquez, C. S.; Fox, G. A.; Broderick, W. E.; Andersen, K; Anderson, O. P.; Barrett, A. G. M.; Hoffman, B. M. J. Am. Chem. Soc. 1992, 114, 7416-7424). Comparison of the crystal structures of 1,2a, and aquo(octakis(methylthio)porphyrazinato)magnesium(II) (Mg(omtp)), a structurally unconstrained reference compound with eight peripheral methylthio groups, shows that [Ni(pzot)]8- adjusts to accommodate either the (S-S) or (S-N-S) modes of coordinating the metal ions at the periphery by a swing of the C(beta)-S bond. H-1 and P-31 NMR studies have been used to determine the nature of the coordination of the Ni(P-P) units to the [Ni(pzot)]8- macrocycle in solution. Model compounds were synthesized as structural references to mimic both possible coordination sites of the [Ni(pzot)]8- ligand. The H-1 and P-31 NMR chemical shifts of macrocycles 2a-d and their respective bidentate model complexes clearly indicate that the macrocycle in solution also binds the Ni(P-P) units in a bidentate fashion. The electronic absorption spectra of complexes 2a-d show a red-shift of the absorbance in the Q-band region due to interaction of the porphyrazine pi-system with the four peripheral metal ions.