gold(III)(methoxide)(κ3-(2,6-((C6H3)t-Bu)2pyridine)) | 1384526-45-7

• 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: gold(III)(methoxide)(κ3-(2,6-((C6H3)t-Bu)2pyridine))
• CAS: 1384526-45-7
• 化学式: C₂₆H₃₀AuNO
• 分子量: 569.497
• InChiKey: JBABFWWJJADYLF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  1,2,4,5-四氟苯 、 gold(III)(methoxide)(κ3-(2,6-((C6H3)t-Bu)2pyridine)) 以 甲苯 为溶剂， 生成 gold(III)(2,3,5,6-tetrafluorophenyl)(κ3-(2,6-((C6H3)t-Bu)2pyridine))
  参考文献：
  名称：

  Cyclometallated gold(iii) hydroxides as versatile synthons for Au–N, Au–C complexes and luminescent compounds

  摘要：

  氢氧化金（III）γ3-(C∧N∧C)*Au(OH)与C–H和N–H化合物以及芳基硼酸反应，可高产量地生成一系列全氟芳基、N杂环和炔基化合物；其中一些化合物在光致发光方面表现出从黄色到蓝色的出乎意料的强烈调制效果[(C∧N∧C)* = 2,6-(C6H3But)2pyridine]。

  DOI：

  10.1039/c2cc33104g
• 作为产物：
  描述：

  (2,6-bis(4-tBuC6H3)2pyridine dianion)AuCl 以 甲醇 、 二氯甲烷 为溶剂， 生成 gold(III)(methoxide)(κ3-(2,6-((C6H3)t-Bu)2pyridine))
  参考文献：
  名称：

  Cyclometallated gold(iii) hydroxides as versatile synthons for Au–N, Au–C complexes and luminescent compounds

  摘要：

  氢氧化金（III）γ3-(C∧N∧C)*Au(OH)与C–H和N–H化合物以及芳基硼酸反应，可高产量地生成一系列全氟芳基、N杂环和炔基化合物；其中一些化合物在光致发光方面表现出从黄色到蓝色的出乎意料的强烈调制效果[(C∧N∧C)* = 2,6-(C6H3But)2pyridine]。

  DOI：

  10.1039/c2cc33104g

文献信息

• Formation of Gold(III) Alkyls from Gold Alkoxide Complexes
  作者：Isabelle Chambrier、Dragoş-Adrian Roşca、Julio Fernandez-Cestau、David L. Hughes、Peter H. M. Budzelaar、Manfred Bochmann

  DOI：10.1021/acs.organomet.7b00077

  日期：2017.4.10

  The gold(III) methoxide complex (C<^>N<^>C)AuOMe (1) reacts with tris(p-tolyl)phosphine in benzene at room temperature under O abstraction to give the methylgold product (C<^>N<^>C)AuMe (2) together with O=P(p-tol)(3) ((C<^>N<^>C) = [2,6-((C6H3Bu)-Bu-t-4)(2)pyridine](2-)). Calculations show that this reaction is energetically favorable (Delta G = -32.3 kcal mol(-1)). The side products in this reaction, the Au(II) complex [Au(C<^>N<^>C)](2) (3) and the phosphorane (p-tol)(3)P(OMe)(2), suggest that at least two reaction pathways may operate, including one involving (C<^>N<^>C)Au-center dot radicals. Attempts to model the reaction by DFT methods showed that PPh3 can approach 1 to give a near-linear Au-O-P arrangement, without phosphine coordination to gold. The analogous reaction of (C<^>N<^>C)AuOEt, on the other hand, gives exclusively a mixture of 3 and (p-tol)(3)P(OEt)(2). Whereas the reaction of (C<^>N<^>C)AuOR (R = Bu-t, p-C6H4F) with P(p-tol)(3) proceeds over a period of hours, compounds with R = CH2CF3, CH(CF3)(2) react almost instantaneously, to give 3 and O=P(p-tol)(3). In chlorinated solvents, treatment of the alkoxides (C<^>N<^>C)AuOR with phosphines generates [(C<^>N<^>C)Au(PR3)]Cl, via Cl abstraction from the solvent. Attempts to extend the synthesis of gold(III) alkoxides to allyl alcohols were unsuccessful; the reaction of (C<^>N<^>C)AuOH with an excess of CH2=CHCH2OH in toluene led instead to allyl alcohol isomerization to give a mixture of gold alkyls, (C<^>N<^>C)AuR' (R' = -CH2CH2CHO (10), -CH2CH(CH2OH)OCH2CH=CH2 (11)), while 2-methallyl alcohol affords R' = CH2CH(Me)CHO (12). The crystal structure of 11 was determined. The formation of Au-C instead of the expected Au-O products is in line with the trend in metal-ligand bond dissociation energies for Au(III): M-H > M-C > M-O.