Tunable Triazole-Phosphine-Copper Catalysts for the Synthesis of 2-Aryl-1<i>H</i>
-benzo[d]imidazoles from Benzyl Alcohols and Diamines by Acceptorless Dehydrogenation and Borrowing Hydrogen Reactions
作者:Zhaojun Xu、Duo-Sheng Wang、Xiaoli Yu、Yongchun Yang、Dawei Wang
DOI:10.1002/adsc.201700179
日期:2017.10.4
activity. Mechanistic studies and deuterium labeling experiments indicated that the reactions proceeded by an initial and reversible alcohol dehydrogenation resulting in a copper hydride intermediate. This was also supported by the direct observation of a diagnostic copper hydride signal by solid‐state infrared spectroscopy. The TAP−Cu‐H complex showed absorptions at 912 cm−1 that could be assigned
三唑-膦-铜配合物(TAP-Cu)已被合成并用作可调谐和有效的催化剂,用于选择性合成氟代2-芳基-1 H-苯并[d]咪唑和1-苄基-2-芳基1小时一步法制得的简单醇中的苯并[d]咪唑衍生物。TAP-Cu对脱氢和借用氢反应均显示出优异且可调节的催化活性,首次证明了80多个例子。观察到配体在催化剂活性中起关键作用。机理研究和氘标记实验表明,反应是通过初始且可逆的醇脱氢进行的,从而生成氢化铜中间体。固态红外光谱法直接观察氢化铜诊断信号也支持了这一点。TAP-Cu-H络合物在912 cm -1处显示吸收可以分配给氢化铜拉伸。此外,也成功地进行了中间双亚胺的直接捕集。
Lewis-base adducts of Group 1B metal(<scp>I</scp>) compounds. Part 16. Synthesis, structure, and solid-state phosphorus-31 nuclear magnetic resonance spectra of some novel [Cu<sub>4</sub>X<sub>4</sub>L<sub>4</sub>](X = halogen, L = N, P base)‘cubane’ clusters
作者:Jeffrey C. Dyason、Peter C. Healy、Lutz M. Engelhardt、Chaveng Pakawatchai、Vincent A. Patrick、Colin L. Raston、Allan H. White
DOI:10.1039/dt9850000831
日期:——
2.874(5)–3.164(4) and I ⋯ I 4.234(2)–4.496(3)Å. All adducts of stoicheiometry [M4X4(PPh3)4](M = Cu or Ag; X = Cl, Br, or I) have now been synthesized and structurally characterized in a cubane configuration. Recrystallization of copper(I) chloride and bromide from triethylamine also yields tetrameric cubane 1 : 1adducts [X = Cl (2) or Br (3)], as does the reaction of copper(I) chloride with the very
从甲苯中重结晶[Cu 4 l 4(PPh 3)4 ]得到该化合物的新多晶型物(1),单晶X射线衍射分析表明该化合物具有四金属“古巴”结构,而不是预期的“步骤”结构。晶体是单斜晶体,空间群P 2 1 / n,a = 19.47(1),b = 26.94(1),c = 13.528(5)Å,β= 98.98(4)°,Z = 4个四聚体; N o的R为0.06= 3681。Cu–I距离范围为2.653(3)至2.732(3)Å,其中Cu⋯Cu 2.874(5)–3.164(4)和I⋯I 4.234(2)–4.496(3)Å。现在已经合成了化学计量学的所有加合物[M 4 X 4(PPh 3)4 ](M = Cu或Ag; X = Cl,Br或I),并在古巴构造中进行了结构表征。从三乙胺中重结晶氯化铜(I)和溴化物也可生成四聚体古巴比1:1的加合物[X = Cl(2)或Br(3)],氯化铜(I)与非常
Hardt, H. D.; Stoll, H.-J., Zeitschrift fur Anorganische und Allgemeine Chemie
作者:Hardt, H. D.、Stoll, H.-J.
DOI:——
日期:——
Reactions of Potassium Bis(phosphinimino)methanide with Group 11 Compounds
作者:Tarun K. Panda、Peter W. Roesky、Patrick Larsen、Shuang Zhang、Claudia Wickleder
DOI:10.1021/ic060932p
日期:2006.9.1
Transmetalation of the potassium methanide complex, K CH(PPh2NSiMe3)(2)}, with [(Ph3P)(2)CuI] afforded the corresponding copper complex [CH(PPh2NSiMe3)(2)} CuPPh3] (1), whereas the reaction of K CH(PPh2NSiMe3) 2} with [Ph3PAuCl] resulted in the dinuclear gold complex [(Ph3PAu)(2) C(PPh2NSiMe3)(2)}] (2). The solid-state structure of 1 shows the formation of a six-membered metallacycle (N1-P1-C1-P2-N2-Cu) that has a twist boat conformation. In contrast, compound 2 is an alpha, alpha-diaurated species, in which the two gold atoms are coordinated in a linear fashion onto the ligand backbone. Photoluminescence measurements show that the latter compound has a strong violet emission.