2-(tricarbonyl(η⁶-2'-methylphenyl)chromium(0))pyridine | 881636-98-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 2-(tricarbonyl(η⁶-2'-methylphenyl)chromium(0))pyridine
• 英文别名: carbon monoxide;chromium;2-(2-methylphenyl)pyridine
• CAS: 881636-98-2
• 化学式: C₁₅H₁₁CrNO₃
• 分子量: 305.253
• InChiKey: JWUXDSVQLLXFAG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.94
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  15.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  bis[(tricarbonyl(η6-phenyl-κC(1))chromium(0))pyridine-κN]mercury(II) 、 碘甲烷 在 n-C₄H₉Li 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以35%的产率得到2-(tricarbonyl(η⁶-2'-methylphenyl)chromium(0))pyridine
  参考文献：
  名称：

  Synthesis of syn-facial (Cr,Mn) benzyl complexes by the stereoselective thermolytic coupling of unsymmetric diazomethanes with cyclomanganated (η6-arene)tricarbonylchromium complexes

  摘要：

  The heat-promoted reaction of 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene with cyclomanganated 2-[tricarbonyl(eta(6)-phenyl)chromium]pyridine afforded, upon departure of a molecule of CO, a new stable manganese alkylidene complex in which, according to X-ray diffraction analyses, the heterocyclic ligand is anti-facial with respect to the Cr(CO)(3) moiety. Similar heat-promoted reactions of unsymmetrically substituted diazoalkanes such as (Me3Si)(H)CN2, (Ph)(Me)CN2, (Ph)(t-Bu)CN2 and (Ph)(FcCH(2)CH(2))CN2, which are precursors of more electrophilic alkylidenes, with cyclomanganated 2-[tricarbonyl(eta(6)-phenyl)chromium]pyridine derivatives afforded new syn-facial heterobimetallic benzyl complexes. The stereoselectivity of these reactions depends on the steric demand of the substituents at the diazoalkane. A phenyl substituent at the diazoalkane favors the formation of syn-facial heterobimetallic benzyl complexes with the Ph group in the endo position. Combining this "phenyl directing effect" to the steric effect operated by a bulky group at the phenyldiazoalkane, like noticed with (Ph)(t-Bu)CN2, led to total stereoselectivity. This study discloses four new X-ray structures of syn-facial Cr,Mn benzyl complexes, which all present the same short Cr-to-Mn distance of ca. 3.04 angstrom. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2005.10.029

文献信息

• Stoichiometric C–H arylation of tricarbonyl(arene)chromium complexes bearing pyridine directing groups
  作者：Matthew J. Fuchter、Dilraj K. Judge、Marko Weimar、Andrew J. P. White

  DOI：10.1039/c3dt50187f

  日期：——

  Differentially substituted Cr(CO)3-complexed aryl pyridines have been shown to readily undergo stoichiometric palladation and subsequent arylation using boronic acid nucleophiles. The positioning of the aryl substituents has been shown to be key in governing substrate reactivity, whereby sterically congested compounds prevent the geometry required for cyclometallation.

  已显示差异取代的Cr（CO）3络合的芳基吡啶易于经历化学计量的palpalation和随后的芳基化硼酸亲核试剂。已经显示出芳基取代基的位置对于控制底物反应性是关键的，由此空间上拥挤的化合物阻止了环金属化所需的几何形状。