W(CO)5(piperidine) | 31082-68-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: W(CO)5(piperidine)
• 英文别名: (η1-piperidine) pentacarbonyl tungsten(0)；Carbon monoxide;piperidine;tungsten；carbon monoxide;piperidine;tungsten
• CAS: 31082-68-5
• 化学式: C₁₀H₁₁NO₅W
• 分子量: 409.051
• InChiKey: XQWZTTBNTWUVDZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.57
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  17
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  W(CO)5(piperidine) 在 四氢呋喃 作用下， 以 四氯乙烯 为溶剂， 生成 pentacarbonyl(piperidine)tungsten*tetrahydrofuran
  参考文献：
  名称：

  Kinetic studies of ligand substitution reactions and general-base catalysis in amine-ligand exchange processes for Group 6B metal carbonyl amine derivatives. Kinetic and spectroscopic evidence for hydrogen-bonded intermediates

  摘要：

  DOI：

  10.1021/ic50226a029
• 作为产物：
  描述：

  哌啶 、 六羰基钨 以 甲基环己烷 为溶剂， 生成 W(CO)5(piperidine)
  参考文献：
  名称：

  Photophysics and photochemistry of pentacarbonyl(pyridine)tungsten(0) complexes which luminesce in fluid solution

  摘要：

  DOI：

  10.1021/ja00378a005

文献信息

• Electrochemistry and [60]fullerene displacement reactions of (dihapto-[60]fullerene) pentacarbonyl metal(<scp>0</scp>) (M = Cr, Mo, W)
  作者：Elvin Igartúa-Nieves、Yessenia Ocasio-Delgado、María D. L. A. Torres-Castillo、Omar Rivera-Betancourt、José A. Rivera-Pagán、Diana Rodriguez、Gustavo E. López、José E. Cortés-Figueroa

  DOI：10.1039/b618260g

  日期：——

  Cyclic voltammetry (CV) measurements on (η2-C60)M(CO)5 complexes (M = Cr, Mo, W) in dichloromethane show three [60]fullerene-centered and reversible reduction/oxidation waves. The E1/2 values of these waves are shifted to positive values relative to the corresponding values of the uncoordinated [60]fullerene in the same solvent. A Jahn–Teller type distortion of the spherical surface of [60]fullerene promoted by [60]fullerene–metal π-backbonding may explain the observed positive shifts. Lewis bases (L = piperidine and triphenyl phosphine) displace [60]fullerene from (η2-C60)M(CO)5 complexes. Analysis of the activation parameters for the metal–[60]fullerene dissociation, the metal–[60]fullerene bond enthalpies (from DFT computations), and metal–solvent (benzene) bond enthalpies (from DFT computations) suggests appreciable solvent contribution to the transition state leading to formation of the intermediate species solvent–M(CO)5. Appreciable transition state stabilization due to solvation of the intermediate species is inferred for M = Mo and W. For M = Cr, stabilization of the intermediate species due to solvation is not accompanied by the corresponding transition state stabilization.

  在二氯甲烷中对 (η2-C60)M(CO)5 复合物（M = Cr、Mo、W）进行的循环伏安（CV）测量显示出三个以 [60] 富勒烯为中心的可逆还原/氧化波。与同一溶剂中未配位的 [60] 富勒烯的相应值相比，这些波的 E1/2 值偏向正值。[60]富勒烯的球形表面在[60]富勒烯-金属 π 反键作用的促进下发生了贾恩-泰勒（Jahn-Teller）型畸变，这可以解释所观察到的正偏移。路易斯碱（L = 哌啶和三苯基膦）将[60]富勒烯从 (η2-C60)M(CO)5 复合物中置换出来。对金属-[60]富勒烯解离的活化参数、金属-[60]富勒烯键焓（来自 DFT 计算）和金属-溶剂（苯）键焓（来自 DFT 计算）的分析表明，溶剂对过渡态有明显的贡献，导致形成中间物种溶剂-M(CO)5。对于 M = Mo 和 W，由于中间产物的溶解，可以推断出明显的过渡态稳定。对于 M = Cr，由于溶解而导致的中间产物稳定并没有伴随相应的过渡态稳定。
• A novel dianionic seven-coordinate complex of tungsten(II), [WCl3(GeCl3)(CO)3]2−: Synthesis, spectroscopic properties and X-ray crystal structure
  作者：Anna Malinowska、Marcin Górski、Andrzej Kochel、Teresa Szymańska-Buzar

  DOI：10.1016/j.inoche.2007.07.027

  日期：2007.10

  Abstract A new dianionic complex of tungsten(II), [(WCl3(GeCl3)(CO)3]2− (12−), containing the piperidinium cations [Hpip]+ as the counter ions, has been obtained from the reaction between [W(CO)4(pip)2] and GeCl4 in dichloromethane solution, and its molecular structure has been elucidated by single-crystal X-ray diffraction studies. The chemical properties of complex 1 were investigated by IR and NMR

  摘要 [(WCl3(GeCl3)(CO)3]2− (12−​​)) 含有哌啶鎓阳离子 [Hpip]+ 作为抗衡离子，通过 [(WCl3(GeCl3)(CO)3]2−) W(CO)4(pip)2]和GeCl4在二氯甲烷溶液中，其分子结构已通过单晶X射线衍射研究阐明。配合物1的化学性质通过溶液中的红外和核磁共振光谱研究。
• Ligand Behavior of a (<i>Z</i>)-Phosphazide (a 1,2,3,4λ⁵-Triazaphosphinine) and of the Corresponding Phosphazene (a 1,2λ⁵-Azaphosphete)
  作者：Klaus Bieger、Ghenwa Bouhadir、Régis Réau、Françoise Dahan、Guy Bertrand

  DOI：10.1021/ja9531440

  日期：1996.1.1

  1,2,3,4 lambda(5)-Triazaphosphinine 1 reacts with PdCl2(PhCN)(2) and W(CO)(5)(THF) at room temperature, affording, according to P-31 NMR spectroscopy, eta(1)-triazaphosphinine complexes 3 and 5, which after elimination of dinitrogen give the bis(eta(1)-azaphosphete)palladium(II) complex 4 and (eta(1)-azaphosphete)W(CO)(5) complex 6, in 65% and 88% yield, respectively. Complex 4 can also be obtained in 90% yield by addition of PdCl2(PhCN)(2) to 1,2 lambda(5)-azaphosphete 2. Addition of cis-Mo(CO)(4)(pip)(2) to 1 leads to (eta(1)-triazaphosphinine)Mo(CO)(4)(pip) complex 7, which was isolated in 70% yield. In solution, at room temperature for 2 days, 7 transforms into to eta(1)-(five-membered cyclophosphazene)Mo(CO)(5) complex 9 in 45% yield. When 2 equiv of W(CO)(5)(pip) is added to 1, complex 10 featuring a five-membered cyclophosphazene bonded to W(CO)(5)(pip) via a hydrogen bond is isolated in 80% yield. 1,2 lambda(5)-Azaphosphete 2 reacts with piperidine, affording five-membered phosphazene ring 11 in 95% yield, which by subsequent treatment with Mo(CO)(5)(pip) and W(CO)(5)(pip) gives complexes 9 (75% yield) and 10 (83% yield), respectively. Schwartz's reagent reacts with 1, affording five-membered zirconacyclophosphazene 12 in 45% yield. Complexes 4, 7, 10, and 12 are characterized by single-crystal X-ray analyses. These results as a whole demonstrate that in contrast with (E)-phosphazides which behave as four-electron donors via the alpha- and gamma-nitrogen atoms and which are stabilized by complexation, (Z)-phosphazides, such as the 1,2,3,4 lambda(5)-triazaphosphinine 1, act as two-electron donors via the beta-nitrogen atom, and are destabilized by the metal with respect to nitrogen elimination.
• Wieland; Van Eldik, Organometallics, 1991, vol. 10, # 9, p. 3110 - 3114
  作者：Wieland、Van Eldik

  DOI：——

  日期：——
• A convenient general route to a series of diphosphine-bridged heterobinuclear complexes that contain rhodium and structures of the mixed-valent complexes [RhM(CO)4(Ph2PCH2PPh2)2] (M = Mn, Re)
  作者：David M. Antonelli、Martin Cowie

  DOI：10.1021/om00156a022

  日期：1990.6