[(2,6-bis(4-tert-butylphenyl)pyridine(-2H))Au]₂ | 1416904-01-2

• 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-tert-butylphenyl)pyridine(-2H))Au]₂
• CAS: 1416904-01-2
• 化学式: C₅₀H₅₄Au₂N₂
• 分子量: 1076.93
• InChiKey: GYQFORKBMBKLBV-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：

  [(2,6-bis(4-tert-butylphenyl)pyridine(-2H))Au]₂ 以 氘代苯 为溶剂， 反应 24.0h， 生成
  参考文献：
  名称：

  AuII钳配合物的光化学歧化：AuI4AuIII4大环的合成与结构

  摘要：

  The Au(II) (CNC)-N-boolean AND-C-boolean AND pincer complex [((CNC)-N-boolean AND-C-boolean AND)Au](2) is stable under thermal conditions but disproportionates on irradiation in solution to give an Au(I)(4)Au(III)(4) mixed-valence aggregate with a 20-membered macrocyclic structure, consisting of four linear Au(I) C-Au-N building blocks, each of which is decorated with a square planar ((CNC)-N-boolean AND-C-boolean AND)Au(III) substituent. In the crystal, the rings are stacked to form solvent-filled channels with an internal diameter of 8.3 angstrom and a cross-channel Au-I center dot center dot center dot Au-I distance of 7.7 angstrom.

  DOI：

  10.1021/acs.organomet.5b00846
• 作为产物：
  描述：

  2,6-bis(4-tert-butylbenzene-6-id-1-yl)pyridine;gold(3+);2-methylpropan-2-olate 在 三对苯甲基膦 作用下， 以 氘代苯 为溶剂， 反应 72.0h， 生成 [(2,6-bis(4-tert-butylphenyl)pyridine(-2H))Au]₂
  参考文献：
  名称：

  由金醇盐配合物形成烷基金 (III)

  摘要：

  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.

  DOI：

  10.1021/acs.organomet.7b00077

文献信息

• A Thermally Stable Gold(III) Hydride: Synthesis, Reactivity, and Reductive Condensation as a Route to Gold(II) Complexes
  作者：Dragoş-Adrian Roşca、Dan A. Smith、David L. Hughes、Manfred Bochmann

  DOI：10.1002/anie.201206468

  日期：2012.10.15

  Going for gold: The first thermally stable gold(III) hydride [(C N C)*AuH] is presented. It undergoes regioselective insertions with allenes to give gold(III) vinyl complexes, and reductive condensation with [(C N C)*AuOH] to the air‐stable AuII product, [(C N C)*2Au2], with a short nonbridged gold–gold bond.

  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。