W(CO)5(2-aminopyridine) | 332839-98-2

• 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: W(CO)5(2-aminopyridine)
• 英文别名: tungsten pentacarbonyl 2-aminopyridine；[W(CO)5(2-aminopyridine)]；[W(CO)5(2-ampy)]；W(CO)5(2APH)；Carbon monoxide;pyridin-2-amine;tungsten
• CAS: 332839-98-2
• 化学式: C₁₀H₆N₂O₅W
• 分子量: 418.018
• InChiKey: UZIZHCWYNBBNKU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.47
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  43.9
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  六羰基钨 以 二氯甲烷 、 二乙二醇 为溶剂， 反应 72.0h， 生成 W(CO)5(2-aminopyridine)
  参考文献：
  名称：

  含M（CO）5的CO释放分子的合成，毒性和生物分布（M = Mo，W和Cr）

  摘要：

  一系列CO释放分子M（CO）的5  L（M = Mo，W和Cr）的，（1，2，3，L =甘氨酸甲酯; 4，5，6，Ñ甲基咪唑; 7，8，9，2-氨基吡啶; 10，11，12，3-氨基吡啶; 13，14，15，4-氨基吡啶），合成。所有配合物均已通过NMR，IR和电喷雾电离质谱进行了表征。14和15的八面体结构也通过X射线晶体学确定。此外，评估了所有复合物的毒性，药代动力学和代谢过程。通过MTT测定对成纤维细胞系增殖的细胞毒性作用。在络合物中，Mo络合物1显示出最低的细胞毒性（IC 50  = 597 µmol l -1），W络合物2显示出显着的毒性作用，IC 50  = 52 µmol l -1。在具有相同配体的情况下，配合物的毒性作用按金属元素W

  DOI：

  10.1002/aoc.3105

文献信息

• An Experimental and Theoretical Investigation of the Carbon Dioxide Insertion Process into the Tungsten−Nitrogen Bond of an Anionic W(0) Complex
  作者：Donald J. Darensbourg、Brian J. Frost、David L. Larkins

  DOI：10.1021/ic001006s

  日期：2001.4.1

  deprotonated amido analogue, W(CO)5(2AP)-. Furthermore, both forms of W(CO)5(2AP)- were found to be more stable than the chelated tungsten tetracarbonyl anion plus CO. On the other hand, CO2 insertion into the W(CO)4(2AP)- anion to provide the chelated carbamate, W(CO)4(OC(O)2AP)-, was thermodynamically favored by >110 kJ/mol. Finally, both experimental and theoretical studies were inconclusive with regard

  由光生成的W（CO）5THF和2APH制备与吡啶结合的五羰基钨的2-氨基吡啶（2APH）衍生物。氢化钠对远端胺基进行质子化反应提供了两种络合物，[Na] [W（CO）5（2AP）]和[Na] 2 [W（CO）4（2AP）] 2。两种配合物均已通过X射线晶体学表征，单体衍生物以其[Na2（18-crown-6）] [W（CO）5（2AP）] 2盐结晶，并表现出较强的Na + ...- NH相互作用。在THF中存在过量的2-氨基吡啶的情况下，W（CO）6的光解作用导致螯合的中性衍生物W（CO）4（2APH）.2APH的有效合成，其中多余的2APH与氢键合其绑定的对应物。通过水洗几乎定量地除去了2-氨基吡啶的溶剂化分子。W（CO）4（2APH）用NaH脱质子化得到酰胺基吡啶衍生物，该衍生物显示出与CO2快速反应生成螯合的氨基甲酸酯络合物W（CO）4（OC（O）2AP）-。但是，由于在与 反应
• Tipping the energy balance toward exocyclic-amino coordination of W(CO)5 by methylation of the amino group of 2- and 4-aminopyridines, but not with adenosine
  作者：Thomas W Stringfield、Rex E Shepherd

  DOI：10.1016/s0020-1693(02)01189-1

  日期：2003.1

  2-Aminopyridine (2-ampy) substitutes on [W(CO)(5)(acetone)] or [W(CO)(5)(thf)] to produce 100% endocyclic N-1 coordinated [W(CO)(5)(2-ampy)]. Both N-1 coordinated and exocyclic-amine-bound isomers of [W(CO)(5)(4-ampy)] are formed by the substitution of 4-aminopyridine (4-ampy) on [W(CO)(5)(acetone)] in the ratio of 58% exo-amine coordination: 42% endocyclic amine under kinetic control. The distribution adjusts by linkage isomerism over 15 days to >86% exo-amine bound for the thermodynamic distribution. Within limit of H-1 NMR detection >95% exo-amine coordination occurs for 4-(dimethylamino)pyridine (4-Me(2)ampy), in spite of increased steric hindrance. Coordination of 2-(dimethylamino)pyridine to W(CO)(5) occurs only as the exo-amine donor, reversing the observations of the 2-ampy case. Coordination of W(CO)(5) with adenosine takes place with purine ring N donors (45% N-1, 33% N-3, and 22% N-7). The monomethylated N-6-methyladenosine produced only N-1 coordination in low yield. Apparently steric blocking by the N-6-methyl group retards coordination at N-7, and hydrogen bonding of the 5'- alcohol to N-3 of the purine ring in response to enhanced basicity of the N-3 site upon methylation of the exo-amine retards addition at N-3 for [W(CO)(5)(N(methyl adenosine)]. Surprisingly in relation to the effects of amino methylation for the simple aminopyrimidines where W(CO)(5) adopts >91% of 2-ampym and 100% of 4-ampym coordination via the exo-amine, N-1 is the preferred site of coordination for adenosines over the exo-amine position. The known releasing effect of the five-member portion of the adenine ring, enhancing 6 basicity at N-1 is not overcome by N-6-methylation which directs much of its enhancement of ring basicity to N-3. N-6,N-6-Dimethyladenosine produced no coordination with W(CO)(5) under equivalent photosynthetic conditions; the second methyl group only provides additional steric hindrance to coordination at N-1, showing the powerful influence of conjugation of the amino lone pair with the purine ring in preventing a sufficiently basic exo-amine that can coordinate W(CO)(5) in contrast to the outcome with the analogous pyridine (2-Me(2)ampy). Acetylation of 4-ampy (4-acetamidopyridine = 4-Acampy) should favor the pyridyl coordination; however, coordination to the carbonyl group is observed for [W(CO)(5)(4-Acampy)]. (C) 2002 Elsevier Science B.V. All rights reserved.