pentacarbonyl(3-ethoxy-3-phenyl-1,2-propadienylidene)tungsten | 143063-47-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: pentacarbonyl(3-ethoxy-3-phenyl-1,2-propadienylidene)tungsten
• CAS: 143063-47-2
• 化学式: C₁₆H₁₀O₆W
• 分子量: 482.102
• InChiKey: MEZNUNFRNVTCHA-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：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  tungsten pentacarbonyl tetrahydrofuran 、 triethyloxonium fluoroborate 、 1-苯基-2-丙炔-1-酮 在 butyllithium 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以37%的产率得到pentacarbonyl(3-ethoxy-3-phenyl-1,2-propadienylidene)tungsten
  参考文献：
  名称：

  Alkoxy-substituted group 6 allenylidene complexes – Synthesis and properties

  摘要：

  Bis(alkoxy)allenylidene complexes, [(CO)(5)M=C=C=C(OR')OR], as well as mono(alkoxy)allenylidene complexes, [(CO)(5)M=C=C=C(OR')Ph], of chromium and tungsten Lire accessible from propynones [H-C C-C(=O)Ph] or propynoic acid esters [H-C C-C(=O)OR; R = Et, (-)-menthyl, endo-bornyl] by the following reaction sequence: (a) deprotonation of the alkynes, (b) reaction with [(CO)(5)M-THF] (M = Cr, W), and (c) alkylation of the resulting alkynyl metallate, [(CO)(5)M-C C-C(=O)R], with Meerwein salts. Vinylidene complexes, [(CO)(5)M=C=C(R')C(=O)OR], are formed as it by-product by C-beta-alkylation of the alkynyl metallate. Dimethylamine displaces one alkoxy substituent of the bis(alkoxy)allenylidene complexes to give dimethylamino(alkoxy)allenylidene complexes, [(CO)(5)M=C=C=C(OR)NMe2]. The analogous reaction of dimethylamine with a mono(alkoxy)-substituted allenylidene complex affords the aminoallenylidene complex [(CO)(5)Cr=C=C=C(NMe2)Ph]. When the amine is used in large excess, the alpha,beta-unsaturated aminocarbene complex [(CO)(5)Cr=C(NMe2)-C(H)=C(NMe2)Ph] is additionally formed by addition of the amine across the C-alpha-C-beta-bond of the allenylidene ligand. The reaction of [(CO)(5)M=C=C=C(OEt)(2)] with dimethyl ethylenediamine offers access to bis(amino)allenylidene complexes, in which C-gamma is part of a five-membered heterocycle. Photolysis of bis(alkoxy)allenylidene complexes in the presence of triphenylphosphine yields tetracarbonyl- and tricarbonyl{bis(phosphine)}allenylidene complexes. Diethylaminopropyne inserts into the C-beta=C-gamma bond Of [(CO)(5)M=C=C=C(OEt)OMethyl] to give alkenylallenylidene complexes. Subsequent acid-catalyzed intramolecular cyclization affords a pyranylidene complex. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2005.08.010

文献信息

• Aumann, Rudolf, Chemische Berichte, 1992, vol. 125, # 12, p. 2773 - 2778
  作者：Aumann, Rudolf

  DOI：——

  日期：——
• Alkoxy-substituted group 6 allenylidene complexes – Synthesis and properties
  作者：Normen Szesni、Bernhard Weibert、Helmut Fischer

  DOI：10.1016/j.ica.2005.08.010

  日期：2006.1

  Bis(alkoxy)allenylidene complexes, [(CO)(5)M=C=C=C(OR')OR], as well as mono(alkoxy)allenylidene complexes, [(CO)(5)M=C=C=C(OR')Ph], of chromium and tungsten Lire accessible from propynones [H-C C-C(=O)Ph] or propynoic acid esters [H-C C-C(=O)OR; R = Et, (-)-menthyl, endo-bornyl] by the following reaction sequence: (a) deprotonation of the alkynes, (b) reaction with [(CO)(5)M-THF] (M = Cr, W), and (c) alkylation of the resulting alkynyl metallate, [(CO)(5)M-C C-C(=O)R], with Meerwein salts. Vinylidene complexes, [(CO)(5)M=C=C(R')C(=O)OR], are formed as it by-product by C-beta-alkylation of the alkynyl metallate. Dimethylamine displaces one alkoxy substituent of the bis(alkoxy)allenylidene complexes to give dimethylamino(alkoxy)allenylidene complexes, [(CO)(5)M=C=C=C(OR)NMe2]. The analogous reaction of dimethylamine with a mono(alkoxy)-substituted allenylidene complex affords the aminoallenylidene complex [(CO)(5)Cr=C=C=C(NMe2)Ph]. When the amine is used in large excess, the alpha,beta-unsaturated aminocarbene complex [(CO)(5)Cr=C(NMe2)-C(H)=C(NMe2)Ph] is additionally formed by addition of the amine across the C-alpha-C-beta-bond of the allenylidene ligand. The reaction of [(CO)(5)M=C=C=C(OEt)(2)] with dimethyl ethylenediamine offers access to bis(amino)allenylidene complexes, in which C-gamma is part of a five-membered heterocycle. Photolysis of bis(alkoxy)allenylidene complexes in the presence of triphenylphosphine yields tetracarbonyl- and tricarbonylbis(phosphine)}allenylidene complexes. Diethylaminopropyne inserts into the C-beta=C-gamma bond Of [(CO)(5)M=C=C=C(OEt)OMethyl] to give alkenylallenylidene complexes. Subsequent acid-catalyzed intramolecular cyclization affords a pyranylidene complex. (c) 2005 Elsevier B.V. All rights reserved.