(2,6-bis(4-tBuC₆H₃)₂pyridine dianion)AuOH | 1384526-46-8

• 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: (2,6-bis(4-tBuC₆H₃)₂pyridine dianion)AuOH
• 英文别名: (2,6-(C₆H₃Bu^t)₂pyridine)AuOH；[(2,6-bis(4’-tert-butylphenyl)pyridine(-2H))AuOH]；2,6-bis(4-tert-butylbenzene-6-id-1-yl)pyridine;gold(3+);hydroxide
• CAS: 1384526-46-8
• 化学式: C₂₅H₂₈AuNO
• 分子量: 555.47
• InChiKey: CPTODTXZHMPRIV-UHFFFAOYSA-M

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：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (2,6-bis(4-tBuC₆H₃)₂pyridine dianion)AuOH 以 四氢呋喃 、 二氯甲烷-D2 、 甲苯 为溶剂， 反应 0.16h， 生成 [(2,6-bis(4-tert-butylphenyl)pyridine(-2H))Au]₂
  参考文献：
  名称：

  热稳定的氢化金（III）：合成，反应性和还原性缩合反应，可形成金（II）配合物

  摘要：

  追求金：提出了第一个热稳定的氢化金（III）[（C N C）* AuH]。它经历了与烯丙基的区域选择性插入，生成了金（III）乙烯基络合物，并与[（C N C）* AuOH]还原缩合到了空气稳定的Au II产品[（C N C）* 2 Au 2 ]，并带有短的非桥金–金债券。

  DOI：

  10.1002/anie.201206468

文献信息

• Gold(III) Olefin Complexes
  作者：Nicky Savjani、Dragoş-Adrian Roşca、Mark Schormann、Manfred Bochmann

  DOI：10.1002/anie.201208356

  日期：2013.1.14

  Zeise's salt gets company: 185 years after the report of the well‐known platinum(II) ethylene compound, examples of isolable olefin complexes of its isoelectronic neighbor in the periodic table, gold(III), have been prepared (see picture). The complexes are very susceptible towards nucleophilic attack; there is also structural evidence for AuIII–Ag interactions.

  Zeise的盐公司成立：在举世闻名的铂（II）乙烯化合物的报告发表185年后，已准备好其在周期表中等电邻苯二甲酸盐（III）的可分离烯烃络合物的实例（见图）。这些复合物很容易受到亲核攻击。也有Au III- Ag相互作用的结构性证据。
• 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.