Modellreaktionen zur umsetzung von ferrocen-1,1′-dithiol mit Diolefinen: II. Die Säuren- and basenkatalysierten reaktionen von ferrocenthiolen mit aktivierten olefinen
作者:Max Herberhold、Oskar Nuyken、Thomas P.öhlmann
DOI:10.1016/0022-328x(95)05423-m
日期:1995.10
Both ferrocenethiol and ferrocene-1,1′-dithiol, Fe(C5H5)(C5H4SH) and Fe(C5H4SH)2, add to activated olefins to give 1:1 and 1:2 adducts, respectively. The base-catalysed (NEt3) reactions of the monofunctional ferrocenethiol with the mono-olefins methyl methacrylate, methyl vinyl sulfone and benzylidene acetone lead to the expected 1:1 adducts whereas 2:1 adducts are obtained with bifunctional olefins
二茂铁硫醇和二茂铁-1,1'-二硫醇,Fe(C 5 H 5)(C 5 H 4 SH)和Fe(C 5 H 4 SH)2均加到活化的烯烃中以得到1:1和1:2加合物。碱催化(NEt 3)单官能二茂铁硫醇与甲基丙烯酸甲酯,甲基乙烯基砜和亚苄基丙酮的单烯烃反应生成预期的1:1加合物,而双官能烯烃(如二乙烯基砜和二亚苄基丙酮)则获得2:1加合物。相应的双官能二茂铁-1,1'-二硫醇与甲基丙烯酸甲酯,甲基乙烯基酮和亚苄基丙酮形成1:2加合物。为了进行比较,作为脂肪族2二茂铁基乙硫醇,铁(C 5 H ^ 5)(C 5 H ^ 4 CH 2 CH 2 SH),用甲基乙烯基砜和二乙烯基砜反应。在所有情况下,二硫化物的Fc-SS-Fc和FcCH 2 CH 2 SSCH 2还分别形成CH 2 = Fc。二茂铁硫醇和二茂铁-1,1'-二硫醇,Fe(C 5 H 5)(C 5 H 4 SH)和Fe(C 5 H
Tuning the Gap: Electronic Properties and Radical-Type Reactivities of Heteronuclear [1.1.1]Propellanes of Heavier Group 14 Elements
Two heteronuclear [1.1.1]propellanes of group 14, Ge2Si3Mes6 (1) and Sn2Si3Mes6 (2) (Mes = 2,4,6-Me3C6H2), were prepared by reductive coupling of Mes2SiCl2 and GeCl2·dioxane or SnCl2. Both compounds were characterized in detail, including X-raystructure analyses on single crystals. In each case it was found that the E2Si3 cluster core consists of three bridging SiMes2} units and two ligand-free bridgehead
制备了两个杂核[1.1.1]丙炔,第14组,Ge 2 Si 3 Mes 6(1)和Sn 2 Si 3 Mes 6(2)(Mes = 2,4,6-Me 3 C 6 H 2)通过Mes 2 SiCl 2和GeCl 2 ·二恶烷或SnCl 2的还原偶联。两种化合物都有详细的表征,包括对单晶的X射线结构分析。在每种情况下,都发现E 2 Si 3簇芯由三个桥接SiMes 2}单元和两个不含配体的桥头原子(E b)。由于桥接单元大小的不同,桥头原子之间的距离比同核对应的Ge 5 Mes 6和Sn 5 Dep 6(Dep = 2 )短得多(1为0.10Å和2为0.27Å)。文献中已知有,6-Et 2 C 6 H 3)。1和2中的E b ···E b相互作用更强通过使用循环伏安法的电化学研究得到了证实。UV / vis研究以及密度泛函理论(DFT)计算进一步支持了这些发现。一系列同核和异核[1.1.1]丙炔的E
Ferrocene derivatives. Part XVI. The aminomethylation of methylthio- and bismethylthio-ferrocene
作者:G. R. Knox、I. G. Morrison、P. L. Pauson
DOI:10.1039/j39670001842
日期:——
The substitution reactions named in the title give all conceivable products. These have been separated chromatographically, either as such or after reduction of the dimethylaminomethyl to a methyl group. Structures have been assigned to the products on the basis of infrared and proton magnetic resonance spectra, and independent synthesis (in one case). The ratios of isomeric products have been determined
Modellreaktionen zur umsetzung von ferrocen-1,1′-dithiol mit diolefinen: die reaktionen von ferrocenthiolen mit norbornadien und norbornen
作者:Max Herberhold、Oskar Nuyken、Thomas Pöhlmann
DOI:10.1016/0022-328x(91)86275-u
日期:1991.3
Ferrocenethiol and ferrocene-1,-1′-dithiol, Fe(C5H5)(C5H4SH) and Fe(C5H4SH)2 respectively, can be added to both norbornadiene and norbornene in a radical-induced process. The reaction of ferrocenethiol with norbornadiene (1 : 10) in toluene at 70°C gives a mixture of 1 : 1 addition products containing 3-ferrocenylthio-nortricyclane (I) as the main component (ca. 80%)l side-products are the substituted
二茂铁硫醇和二茂铁-1,-1'-二硫醇,Fe(C 5 H 5)(C 5 H 4 SH)和Fe(C 5 H 4 SH)2可以分别在自由基中加入降冰片二烯和降冰片烯-诱导过程。二茂铁硫醇与降冰片二烯(1:10)在甲苯中于70°C反应,得到含有3-二茂铁硫基-三环烷(I)作为主要成分的1:1加合物的混合物(约80%)l副产物为取代的降冰片烯衍生物5- exo-和5-内-二茂铁基硫代降冰片烯(II和III)以及7-抗-二茂铁基硫代降冰片烯-(IV)。仅获得痕量的包含二茂铁硫醇和降冰片二烯的比例为2:1的加成化合物,并通过质谱鉴定。
Organogold complexes of the type [R(AuPPh3)2]+BF−4 (I) containing a univalent gold atom and an AuAu fragment have been synthesised. They are formed by the interaction of RAuPPH3 with tetrafluoroboric acid or organomercury mercury compounds with CH3AuPPh3 and HBF4. Their structures have been identified through 1H NMR, 31P NMR, IR, UV (and X-ray for [C5H5 - FeC5C5H4(AuPPh3)2]+BF−4). When acted upon