pentacarbonyl[(benzyloxy)(methyl)carbene]chromium(0) | 117041-03-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: pentacarbonyl[(benzyloxy)(methyl)carbene]chromium(0)
• 英文别名: pentacarbonyl(methyl(benzyloxy)carbene)chromium(0)；Carbon monoxide;1-phenylmethoxyethylidenechromium
• CAS: 117041-03-9
• 化学式: C₁₄H₁₀CrO₆
• 分子量: 326.226
• InChiKey: VEQXZZXPRZDGEQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.07
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  14.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  pentacarbonyl[(benzyloxy)(methyl)carbene]chromium(0) 以 苯 为溶剂， 以0%的产率得到(η(6)-1-phenylpropan-2-on)chromium tricarbonyl
  参考文献：
  名称：

  Unusual rearrangement of Fischer carbene complexes to ketones

  摘要：

  首次描述了铬和钨的芳基芳基甲氧基炔烃络合物与芳基芳基甲基酮的热重排反应。

  DOI：

  10.1039/c39920000793
• 作为产物：
  描述：

  四甲基铵(1-羟基亚乙基)五羰基铬 、 三甲基乙酰氯 、 苯甲醇 以 二氯甲烷 为溶剂， 以80%的产率得到pentacarbonyl[(benzyloxy)(methyl)carbene]chromium(0)
  参考文献：
  名称：

  五羰基铬卡宾配合物的 Chromium-53 核磁共振研究

  摘要：

  记录了 46 种铬-卡宾配合物的 {sup 53}Cr NMR 光谱，并报告了化学位移和线宽数据，以及相关的红外、紫外可见和 {sup 13}C NMR 光谱数据。{sup 53}Cr 化学位移与卡宾配体的供体-受体性质非常相关，并且对杂原子与卡宾碳的 {pi} 重叠效率的空间影响非常敏感。{delta}({sup 53}Cr) 与亚胺形成{β}-内酰胺的反应性没有相关性，但线宽似乎与反应性有关。初步尝试利用{sup 53}Cr NMR 数据来指导铬-卡宾配合物的合成利用。5 个参考文献，49 个图，1 个标签。

  DOI：

  10.1021/ja00233a018

文献信息

• Control over the <i>E</i>/<i>Z</i> Selectivity of the Catalytic Dimerization of Group 6 (Fischer) Metal Carbene Complexes
  作者：Gong M. Chu、Israel Fernández、Miguel A. Sierra

  DOI：10.1021/jo302130h

  日期：2013.2.1

  additives in the reaction of self-dimerization of alkoxychromium(0) (Fischer) carbene complexes resulted in the selection of Pd(PtBu3)2 to effect this transformation with good to excellent E selectivities and acceptable to excellent chemical yields. This catalyst will allow the control of the geometry in the synthesis of polyconjugated olefins, one emerging application of these catalytic reactions.

  对烷氧基铬（0）（Fischer）卡宾配合物自二聚反应中不同催化剂和添加剂的影响进行系统研究后，选择了Pd（P t Bu 3）2来实现具有良好或优异E的转化。选择性和优良的化学收率是​​可以接受的。该催化剂将允许控制聚共轭烯烃的合成中的几何形状，这些催化反应的一种新兴应用。
• Photoreactions of γ,δ-Unsaturated Chromium Carbene Complexes
  作者：William H. Moser、Louis S. Hegedus

  DOI：10.1021/ja9537585

  日期：1996.1.1

  A number of functionalized γ,δ-unsaturated chromium carbene complexes were synthesized, and their photochemistry was studied. Photolysis of carbene complexes 5 and 17 induced intramolecular [2 + 2] cycloaddition to afford cyclobutanones 6 and 18, respectively. If the photoreactions were not run in thoroughly degassed solvents, small amounts of lactones 7 and 19 were obtained as well. Cyclobutanones

  合成了多种功能化的γ,δ-不饱和铬卡宾配合物，并对其光化学进行了研究。卡宾配合物 5 和 17 的光解诱导分子内 [2 + 2] 环加成，分别得到环丁酮 6 和 18。如果光反应不是在彻底脱气的溶剂中进行，也会得到少量的内酯 7 和 19。环丁酮 6 和 18 分离后稳定，但在酸性溶液中经历酸催化的频哪醇重排/水解转化，得到新型 α-羟基取代的双环 [3.1.0] 己酮化合物 20 和 21。环丙基卡宾配合物 28 的光解诱导涉及光生烯酮部分的乙烯基环丙基重排以提供 α-烷氧基环戊烯酮 29。
• Preparation of Fischer carbene complexes by alkylation of acylmetalates with alkyl iodides
  作者：Thomas R. Hoye、Kejian Chen、James R. Vyvyan

  DOI：10.1021/om00031a056

  日期：1993.7

  Neutral Fischer carbene complexes bearing alkoxy groups as the donor substituents on the carbene carbon atom have been synthesized by direct alkylation of the lithium acylmetalates (formed by classical addition of organolithium compounds to metal hexacarbonyl) by alkyl iodides. It was shown that the reaction proceeds under normal phase-transfer conditions (CH2-Cl2/H2O) or, preferably, in aqueous medium alone. However, in both cases the presence of a catalytic amount of a tetraalkylammonium salt (n-Bu4NBr) was required. Attractive features of this methodology are (i) the economy of using alkyl iodides in place of the usual alkylating agents (like Me3O+BF4-, magic methyl, or methyl triflate), (ii) the procedural ease of ''one-pot'' preparation of the carbene complexes, and (iii) the greater variety of alkyl moieties that can be incorporated as part of the alkoxy substituent using the more readily available alkyl iodides containing nontrivial alkyl groups. The procedure is preparatively useful for accessing chromium-containing carbenes, but yields of the analogous molybdenum- and tungsten-containing species are only less-than-or-equal-to 10%. Mechanistic considerations suggest that products are formed by competing pathways involving direct S(N)2 displacement vs electron-transfer-initiated S(RN)1 processes.
• Aqueous Organometallic Chemistry: Phase-Transfer-Catalyzed Alkylation of Fischer Carbene Complexes
  作者：Sk. Rasidul Amin、Amitabha Sarkar

  DOI：10.1021/om00001a074

  日期：1995.1

  Fischer carbene complexes can be conveniently alkylated, often. with high diastereoselectivity, by reactive halides under biphasic conditions.
• Chromium-53 nuclear magnetic resonance studies of pentacarbonylchromium carbene complexes
  作者：Andreas. Hafner、Louis S. Hegedus、Guy. DeWeck、Bruce. Hawkins、Karl H. Doetz

  DOI：10.1021/ja00233a018

  日期：1988.12

  The sup 53}Cr NMR spectra of 46 chromium-carbene complexes were recorded, and chemical shift and line width data are reported, along with associated infrared, uv-visible, and sup 13}C NMR spectroscopic data. The sup 53}Cr chemical shifts correlated very well with the donor-acceptor properties of the carbene ligand and were quite sensitive to steric influences on efficiency of pi}-overlap of the

  记录了 46 种铬-卡宾配合物的 sup 53}Cr NMR 光谱，并报告了化学位移和线宽数据，以及相关的红外、紫外可见和 sup 13}C NMR 光谱数据。sup 53}Cr 化学位移与卡宾配体的供体-受体性质非常相关，并且对杂原子与卡宾碳的 pi} 重叠效率的空间影响非常敏感。delta}(sup 53}Cr) 与亚胺形成β}-内酰胺的反应性没有相关性，但线宽似乎与反应性有关。初步尝试利用sup 53}Cr NMR 数据来指导铬-卡宾配合物的合成利用。5 个参考文献，49 个图，1 个标签。