(carbon dioxide)bis(tricyclohexylphosphine)nickel | 57307-01-4

• 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: (carbon dioxide)bis(tricyclohexylphosphine)nickel
• 英文别名: {Ni(PCy3)2(η2-CO2)}；Ni(PCy3)2(η2-CO2)；Ni(η2-CO2)(PCy3)2
• CAS: 57307-01-4
• 化学式: C₃₇H₆₆NiO₂P₂
• 分子量: 663.567
• InChiKey: WKVVATBEYVRXSX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.35
• 重原子数：
  42
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.97
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (carbon dioxide)bis(tricyclohexylphosphine)nickel 在 氧气 作用下， 以 solid 为溶剂， 生成 (peroxocarbonato)bis(tricyclohexylphosphine)nickel(II) ne
  参考文献：
  名称：

  （二氧化碳）双（三烷基膦）镍配合物

  摘要：

  [NiL 4 ]（L = PEt 3或PBu n 3）与CO 2在甲苯中的反应通过[Ni（CO 2）L 3 ]物种提供式[Ni（CO 2）L 2 ]的配合物。还报道了[Ni（CO 2）{P（C 6 H 11）3 } 2 ]·0.75C 6 H 5 Me与O 2的反应，生成（过氧羰基）-双（三环己基膦）镍（II）。

  DOI：

  10.1039/dt9770000708
• 作为产物：
  描述：

  [Ni(PCy₃)₂]₂(N₂) 在 二氧化碳 作用下， 生成 (carbon dioxide)bis(tricyclohexylphosphine)nickel
  参考文献：
  名称：

  Reactivity of some transition metal systems toward liquid carbon dioxide

  摘要：

  DOI：

  10.1021/ja00383a026

文献信息

• Selective Reduction of CO₂ to a Formate Equivalent with Heterobimetallic Gold- - -Copper Hydride Complexes
  作者：Alexandra Hicken、Andrew J. P. White、Mark R. Crimmin

  DOI：10.1002/anie.201709072

  日期：2017.11.20

  A series of heterobimetallic complexes containing three‐center, two‐electron Au−H−Cu bonds have been prepared from addition of a parent gold hydride to a bent d10 copper(I) fragment. These highly unusual heterobimetallic complexes represent a missing link in the widely investigated series of neutral and cationic coinage metal hydride complexes containing Cu−H−Cu and M−H−M+ moieties (M=Cu, Ag). The

  通过将母体氢化物加到弯曲的d 10铜（I）片段上，可以制备出一系列包含三中心，两电子Au-H-Cu键的杂双金属配合物。这些高度不寻常的异双金属配合物代表了广泛研究的一系列含有Cu-H-Cu和M-H-M +部分（M = Cu，Ag）的中性和阳离子造币金属氢化物配合物中的缺失环节。定义明确的杂双金属氢化物配合物可将HBpin作为还原剂将CO 2转化为HCO 2 Bpin的预催化剂。杂双金属配合物对甲酸酯当量催化生产的选择性超过了母体单体第11组配合物的选择性。
• Reduction of co-ordinated carbon dioxide to carbon monoxide via protonation by thiols and other Brønsted acids promoted by Ni-systems: a contribution to the understanding of the mode of action of the enzyme carbon monoxide dehydrogenase
  作者：Michele Aresta、Eugenio Quaranta、Immacolata Tommasi

  DOI：10.1039/c39880000450

  日期：——

  Carbon dioxide co-ordinated to Ni0 is easily reduced to bound carbon monoxide by R–SH (R = H, alkyl, benzyl, phenyl, and substituted phenyl) and other Brønsted acids, providing a reasonable model for the Ni-containing enzyme carbon monoxide dehydrogenase.

  通过R–SH（R = H，烷基，苄基，苯基和取代的苯基）和其他布朗斯台德酸，可以容易地将与Ni 0配位的二氧化碳还原为结合的一氧化碳，从而为含Ni的酶碳提供了一个合理的模型一氧化碳脱氢酶。
• Doehring, A.; Jolly, P. W.; Krueger, C., Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1985, vol. 40, # 4, p. 484 - 488
  作者：Doehring, A.、Jolly, P. W.、Krueger, C.、Romao, M. J.

  DOI：——

  日期：——
• Aresta, Michele; Gobetto, Roberto; Quaranta, Eugenio, Inorganic Chemistry, 1992, vol. 31, # 21, p. 4286 - 4290
  作者：Aresta, Michele、Gobetto, Roberto、Quaranta, Eugenio、Tommasi, Immacolata

  DOI：——

  日期：——
• Mechanism of formation of the peroxocarbonate complex (PCy3)2Ni(CO4) from solid (PCy3)2Ni(CO2) and dioxygen: an example of solid-state metallorganic reaction involving CO2 deco-ordination and reinsertion into the OO bond of (PCy3)2Ni(O2). Reactivity of the peroxocarbonate complex towards olefins in the solid state and in solution
  作者：Michele Aresta、Immacolata Tommasi、Angela Dibenedetto、Monique Fouassier、Joelle Mascetti

  DOI：10.1016/s0020-1693(01)00737-x

  日期：2002.3

  Solid (PCY3)(2)Ni(CO2) (1) reacts with dioxygen to afford the peroxocarbonate Complex (PCY3)(2)Ni(CO2) (3). The use of labelled (CO2)-C-13, (CO2-)-O-18 O-18(2), coupled with a FTIR study of both the gas-phase in equilibrium with the solid and the solid resulting complex, allows to propose the reaction mechanism that implies CO2 deco-ordination, O-2, co-ordination, and CO2 insertion into the O-O bond of the newly formed, reactive (PCy3)(2)Ni(O-2) complex 2. A normal mode analysis substantiates the band assignment and the proposed mechanism. Peroxocarbonate (3) exhibits a C-13 resonance at 166.6 ppm and a single P-31 signal at 43.1 ppm below 200 K. The reactivity of the peroxo-group as one-oxygen transfer agent prevents the spectroscopic characterisation of 3 in solution at room temperature. An out-of-sphere phosphine can be easily oxidised. A gaseous olefin. mono-ene (ethylene) or diene (allene), added to 3. makes easier the deco-ordination process of one phosphine ligand, that is then oxidised to phosphine oxide. The gaseous olefin itself is not oxidised until free phosphine is present in the medium. In solution, styrene is oxidised through a two or one-oxygen transfer pathway, according to the reaction condition. (C) 2002 Published by Elsevier Science.