1,3-二(2,6-二甲基苯基)-2-四氢咪唑基-苯亚甲基-二吡啶基-二氯合钌 化合物的合成

设计了由1,3-二(2,6-二甲基苯基)-2-四氢咪唑基-苯亚甲基-三苯基膦-二氯合钌(7)和吡啶反应生成无膦型金属钌卡宾化合物1,3-二(2,6-二甲苯基)-2-四氢咪唑基-苯亚甲基-2-吡啶基-二氯合钌(8), 8作为高效催化剂用于丙烯腈和烯丙基苯的交叉交互置换反应. 新化合物7, 8经核磁共振氢谱、碳谱和高分辨率质谱予以证实.     

2-苯基-4,5-二(2''''-吡啶基)咪唑的合成

以苯甲醛和1,2-(2'-吡啶基)-乙二酮为原料,用德布斯法合成了未见报道的2-苯基-4,5-二(2'-吡啶基)咪唑,收率31%,其结构经1H NMR, IR和MS表征.     

取代四甲基环戊二烯基钌羰基化合物的合成及晶体结构(英文)

The ligands (C5Me4R) [R =n-Butyl (1), Benzyl (2), PhMe-2 (3)] reacted with Ru3(CO)12 in refluxing xylene to give corresponding new substituted tetramethylcyclopentadienyl diruthenium metal carbonyl complexes [(η5-C5Me4R)Ru(CO)( μ-CO)]2 [R=n-Butyl (4), Benzyl (5), PhMe-2 (6)], respectively. The three new complexes were characterized by elemental analysis, IR and 1H NMR spectra. The crystal structure of complex 5 was determined by single crystal X-ray diffraction. The X-ray crystal structure of complex 5 confirms the structure with bridging and terminal CO groups. CCDC: 709601.     

二(1-正丁基茚基)四羰基二钌的合成与晶体结构

由C9H6-n-BuH与Ru3(CO)12在二甲苯中加热回流, 合成了一个新的双核配合物(η5-C9H6-n-Bu)2Ru2(CO)4. 通过元素分析、红外光谱、核磁共振氢谱对其结构进行了表征. 用X射线单晶衍射法测定了(η5-C9H6-n-Bu)2Ru2(CO)4的结构, 结果表明: 晶体属于三斜晶系, Pī空间群, a＝0.8880(5) nm, b＝1.2337(8) nm, c＝1.3235(8) nm, α＝83.054(12)°, β＝76.683(10)°, γ＝77.036(12)°, V＝1.3713(15) nm3, Dc＝1.588 g•cm－3, m＝1.134 mm－1, F(000)＝658, Z＝2, R1＝0.0993, wR2＝0.2459.     

茂基钌化合物的合成与结构研究:双核钌氢合物的合成与晶体结构研究

三氢钌化物[(C~5H~5)Ru(PPh~3)H~3](1)经光解反应生成了一个双核钌氢化合物[(C~5H~5)Ru.(PPh~3)(μ-H)]~2(2).用X射线重原子法及Fourier迭代解出了2的晶体结构,其分子呈二聚形式,Ru-Ru键处在对称中心,两个钌原子间还通过两个桥氢原子相联,该二聚体的单体为16电子物种,与推测的碳氢键活化反应的中间体类似,为金属有机氢化物活化碳氢键的反应历程提供了证据.文中还给出了2的可能形成过程.     

二(四甲基环戊二烯)钌—一个全覆盖型夹心化合物

用“原位”还原四甲基环戊二烯法,合成一新化合物,二(四甲基环戊二烯)钌。X射线衍射研究结果表明,这个化合物的构象是全覆盖型的,晶体属单斜系,C2/c空间群,晶胞参数:a=22.075(3),b=10·674(3),c=14.135(2)(?),β=101.7d(1)°,V=3261.1(?)。Z=8。几轮块矩阵最小二乘修正,得最后R值为0.034。     

三(4-咪唑-2,6-二氯苯基)甲基自由基(TTM-3Im)的合成及其性质研究

本文报道了一种新的三苯甲基自由基衍生物,即三(4-咪唑-2,6-二氯苯基)甲基自由基(TTM-3Im)的合成与性质研究.TTM-3Im展示了有趣的发光性能和良好的稳定性.此外,由于TTM-3Im含有3个咪唑基元,因此可以作为配体用于构筑自由基金属有机框架结构(MOFs).基于此,本工作成功地将稳定发光自由基TTM-3I...     

取代四甲基环戊二烯基钌羰基化合物的合成及结构

将配体[C₅Me₄HR](R=cyclopentyl,cyclohexyl,ⁿPr)分别与Ru₃(CO)₁₂在二甲苯中加热回流,合成了3个新的双核配合物[(η⁵-C₅Me₄R)Ru(CO)(μ-CO)]₂(R=cyclopentyl(1),cyclohexyl(2),ⁿPr(3))。利用红外光谱、元素分析、核磁共振氢谱对它们的结构进行了表征,用X-射线单晶衍射法测定了1和2的结构。     

取代四甲基环戊二烯基钌羰基化合物的合成及结构

将配体[C5Me4HR](R=cyclopentyl,cyclohexyl,nPr)分别与Ru3(CO)12在二甲苯中加热回流,合成了3个新的双核配合物[(η5-C5Me4R)Ru(CO)(μ-CO)]2(R=cyclopentyl(1),cyclohexyl(2),nPr(3))。利用红外光谱、元素分析、核磁共振氢谱对它们的结构进行了表征,用X-射线单晶衍射法测定了1和2的结构。     

2,6-二(5-烷基水杨基)-4-烷基苯酚的合成

以自制的正构长链烷基酚为原料与多聚甲醛在碱性催化剂下进行羟甲基化反应,生成2,6-二羟甲基-4-烷基苯酚,再与另两分子烷基酚在固体超强酸催化下进行缩合反应生成2,6-二(5-烷基水杨基)-4-烷基苯酚,用核磁共振氢谱和碳谱、红外光谱和元素分析对产物进行了结构鉴定,探讨了催化剂、反应物料配比、反应时间等条件对产物产率的影响.另外根据上述反应路线,以工业品壬基酚和多聚甲醛为原料,经羟甲基化反应、缩合反应合成了2,6-二(5-壬基水杨基)-4-壬基苯酚.上述两种结果表明,选用SO24-/SnO2固体超强酸作催化剂,2,6-二羟甲基-4-烷基苯酚和烷基酚的配比为1:2,140℃反应2h,产率达到95%.     

Formation and structure of diruthenium complexes Ru2(CO)6−n (PPh3) n {μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} (n=1, 2)

Ruthenium carbonyl triphenylphosphine complexes Ru₂(CO)_6−n (PPh₃) _n {μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} (n=1, 2) were obtained by the reaction of complex Ru₂(CO)₆{μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} containing the ruthenacyclopentadiene moiety with PPh₃ in refluxing toluene. The complexes were characterized by IR and by¹H,¹³C, and³¹P NMR spectroscopy, and by X-ray analysis. The monophosphine derivative is identical to the complex formed by fragmentation of the Ru₃(CO)₈(PPh₃){μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} cluster and contains the PPh₃ ligand at the ruthenium atom of the ruthenacyclopentadiene moiety. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1836–1843, September, 1998     

2,6-双(对氨基苯基偶氮)-9,10-蒽二酮的合成

从2,6-二氨基蒽醌出发,经亚硝酰硫酸双重氮化,再与苯胺偶合合成了未见文献报道的三阶有机非线性光学材料———2,6-双(对氨基苯基偶氮)-9,10-蒽二酮,收率56.8%。其结构经1H NMR,IR和元素分析确证。     

2,6-双(对羟基苯基偶氮)-9,10-蒽醌的合成

以2,6-二氨基蒽醌为原料,经硝酸钠与盐酸双重氮化制得2,6-二氨基蒽醌双重氮盐(2);2与苯酚偶合合成了未见文献报道的双偶氮类化合物--2,6-双(对羟基苯基偶氮)-9,10-蒽醌(3),其结构经1H NMR,IR,MS和元素分析表征.最佳的偶合反应条件为: 2 2.0 mmol,n(2) ∶ n(苯酚)＝1.0 ∶ 2.5,在pH=9的条件下,于0 ℃～5 ℃反应4 h,3的收率60%.     

2,6-Bis(methylencyclopentadienyl)-pyridin-zirconocen- und -hafnocendichlorid; Bildung und Kristallstruktur von [C5H3N-2,6-(CH2?C5H4)2Zr(Cl)(OH2)]2[ZrCl6]

2,6-Bis(methylenecyclopentadienyl)-pyridine-zirconocene and -hafnocene Dichloride; Formation and Crystal Structure of [C₅H₃N-2,6-(CH₂? C₅H₄)₂Zr(Cl)(OH₂)[ZrCl₆]] Pyridine bridged metallocene dichlorides of type C₅H₃N-2,6-(CH₂? C₅H₄)₂MCl₂ (M = Zr ( 2 ), Hf ( 5 )) were synthesized. The presence of N → Zr interaction favours the formation of zirconocene cations. Traces of water cause the formation of the salt-like compound [C₅H₃N-2,6-(CH₂? C₅H₄)₂Zr(Cl)(OH₂)]₂[ZrCl₆] 4 from 2 . The new compounds were characterized by ¹H n.m.r., and mass spectroscopy. The X-ray crystal structure of 4 shows discrete cations and anions which are connected by H-bridges.     

Crystal structure of ammonium pentachloroaquaruthenate(III) (NH4)2[Ru(H2O)Cl5]

The structure of ammonium pentachloroaquaruthenate was established by X-ray diffraction analysis. The structure was built of the [Ru(H₂O)Cl₅]^2? complex anions and NH ₄ ⁺ cations. The compound was obtained in the form of dark red fine crystals, which are stable on storage in air.     

钛配合物Cp2TiL,Cp2Ti2Cl2(μ-O)和Cp4Ti4Cl4(μ-O)4的合成与晶体结构研究(Cp=η5-C5H5,L=2,6-吡啶二羧酸盐)

利用溶剂热的方法将Cp2TiCl2(Cp=η5-C5H5)与2,6-吡啶二羧酸钠(L)反应,不同的反应时间得到了2个具有不同晶体空间群的化合物Cp2TiL(1a和1b),而在常温或低温下,Cp2TiCl2或CpTiCl3同羧酸盐或亚胺反应却得到了双核或四核氧桥联的钛化合物。     

Synthesis and Crystal Structure of 2,6-Bis（2-pyridinylmethyl）-3,5-bis（2-hydroxyl-5-chlorophenyl）pyrazine

The title compound,2,6-bis(2-pyridinylmethyl)-3,5-bis(2-hydroxyl-5-chlorophe nyl)-pyrazine(C26H12Cl2N4O2C2H8O2,Mr=551.41),has been synthesized and characterized by LC-ESIMS,NMR,UV and IR spectroscopy as well as by X-ray single-crystal diffraction.The compound behaves as a substituted pyrazine.The hydrogen atoms on C(2) and C(3) are substituted by 2-pyridinyl,whereas those on C(1) and C(4) are substituted by 2-hydroxyl-5-chlorophenyl.It crystallizes in the monoclinic system,space group P21/c with a=8.9433(12),b=32.003(4),c=10.5209(18),β=111.199(2)°,V=2807.5(7)3,Z=4,Dc=1.305 mg/m3,F(000)=1144 and μ=0.094 mm-1.A total of 13235 reflections were collected in the range of 2.17～25.01o by using a phi and omega scan mode,of which 4923 were unique(Rint=0.0692) and 2872 observed reflections with Ⅰ > 2σ(Ⅰ) were used in the structure solution and refinement.     

Synthesis and structures of 1,1′-bis(diphenylphosphino)metallocenyl complexes M(η 5-C5H4PPh2)2Ru(H2O)2(OTs)2 (M = Fe, Ru, or Os)

The reaction of equimolar amounts of M(η⁵-C₅H₄PPh₂)₂ (M = Fe, Ru, or Os) and [Ru(H₂O)₆](OTs)₂ afforded the M(η⁵-C₅H₄PPh₂)₂Ru(H₂O)₂(OTs)₂ complexes, which were characterized by elemental analysis and ¹H, ¹³C, and ³¹P NMR spectroscopy. The structure of the osmocene complex was established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 659—661, April, 2006.