二芳基汞的合成

将氯化重氮苯的溶液加入氯化汞、维生素C、丙酮和少量氯化铜的混合物中,得到80％的氯化苯汞;如在反应混合物中补加维生素C、氯化铜和浓氨水,则得到二苯汞。用同样的方法制备了其他的二芳基汞,并讨论了反应可能的机理。     

芳基汞化合物的性质研究 VI.某些氯化芳基汞的紫外吸收光谱

The UV spectra of 24 substituted phenylmercuric chlorides as well as α-and β-naphthylmereuric chlorides were measured in ethanolic solutions. The effects of the substitution group on the C-Hg bond and UV spectral characterisics were discussed.     

芳基汞化合物的性质研究 Ⅵ.某些氯化芳基汞的紫外吸收光谱

本文测定了24种p-,o-,m-取代苯基氯化汞和α-,β-萘基氯化汞在乙醇溶液中的紫外光谱。以苯基氯化汞的吸收带为基准,发现由于对位取代基引起的E吸收带位移增量Δλ(λ_(p-XC_6H_6HgCl)-λ(C_4H_6HgCl))与Hammett取代基常数σ_p间呈现良好的线性关系。作为衡量取代基共轭效应尺度的Δσ(σ_p-σ_m)和Taft参数σ_R均与对位取代苯基氯化汞的E吸收带和B吸收带位移增量呈较好的线性关系所得直线的方向和斜率与取代基的电性有关。对邻位取代苯基氯化汞的吸收光谱进行了讨论。α-,β-萘基氯化汞的紫外光谱的特征表明当HgCl位于β位时,可与萘基发生共轭。     

芳基汞化合物的性质研究(Ⅴ)——某些氯化芳基汞的质谱

本文研究了23种氯化芳基汞XC₆H₄HgCl的质谱。结果证明大多数氯化芳基汞的分子离子峰均较强,且各种氯化芳基汞生成碎片离子D([XC₆H₄]⁺)均较汞-氯键断裂生成碎片离子E([XC₆H₄Hg]⁺)容易,此结果可以看作是汞有机化合物开裂的普遍性规律。取代基的电性对于碎片离子的稳定性和丰度有明显的影响。就多数间、对位取代基而言,代表取代基对生成离子D速度的影响参数log(Z/Z_H)与HammettBrown常数σ⁺之间有良好的线性关系。邻乙酯基苯基氯化汞与间、对位取代物比较,难于发生McLafferty重排,此与分子内配位有关。     

芳基对硝基苯乙炔基汞的合成

采用芳基醋酸汞或芳基氢氧化汞与对硝基苯乙炔在碱性介质中反应,合成了12种新的取代苯基对硝基苯乙炔基汞化合物。紫外可见光诸实验表明此合成反应为可逆反应。通过元素分析及IR、MS、¹NMR和UV光谱对化合物结构进行了鉴定。     

芳基汞化合物的性质研究 Ⅷ.某些对称二取代芳基汞的紫外吸收光谱

本文研究了19种对称二取代芳基汞和二(β-萘基)汞的紫外吸收光谱,与二苯汞的λ_(max)(E)比较,各对称二取代苯汞的λ_(max)(E)均有红移;与相应的取代苯基氯化汞的λ_(max)(E)比较,对称二取代苯汞的λ_(max)(E)有更大红移.说明两个苯环通过汞原子的空p轨道可相互共轭.由简单分子轨道理论计算所得λ_(max)(E)与实验值相符合.     

芳基对硝基苯乙快基汞的合成

采用芳基醋酸汞或芳基氢氧化汞与对硝基苯乙炔在碱性介质中反应，合成了１２种新的取代苯基对硝基苯乙炔基汞化合物。紫外可见光谱实验表明此化合成反应为可逆反应。通过元素分析及ＩＲ，ＭＳ，＾１ＨＮＭＲ和ＵＶ光谱对化合物结构进行了鉴定。     

芳基汞化合物的性质研究;X.氯化邻乙氧羰基苯汞的晶体结构

用Syntex P3四圆衍射仪收集氯化邻乙氧羰基苯汞晶体的三维衍射数据,晶体属单斜晶系;空间群为C2h[5]-P21/c;a=10.611(2)A,b=4.987(1)A,c=19.416(5)A,β=95.74(2);z=4,利用Patterson法和直接法测定了晶体结构,用块矩阵最小二乘法修正后,最终R值为0.044.晶体结构分析表明,在氯化邻乙氧羰基苯汞分子中存在有分子内配位,Hg...O(1)的间距为2.734A。     

含有配位基团的芳基汞化合物的金属转移反应

本文综述了含有配位基团芳基汞化合物与过渡金属和非过渡金属之间的金属转移反应。讨论了底物中的配位基团对于某些金属转移产物形成的影响.     

含有配位基团的芳基汞化合物的金属转移反应

本文综述了含有配位基团芳基汞化合物与过渡金属和非过渡金属之间的金属转移反应。讨论了底物中的配位基团对于某些金属转移产物形成的影响。     

Organoboron compounds. Communication 136. Boron-germanium compounds

Summary Triethyl- and triphenyl-germanes add to dimethyl 2-propene-1-boronate with formation of dimethyl 3-(triethylgermyl)- and 3-(triphenylgermyl)-1-propaneboronates respectively.The NMR spectrum was measured by V. F. Bystrov, whom the authors thank. The authors also thank V. F. Mironov for the provision of a sample of 3-(triethylgermyl)-1-propanol.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 68–72, January, 1965     

Polymerization studies on allylic compounds. IV. Methallylic compounds

The free-radical polymerization of a series of 2-methyl-3-substituted propenes was investigated. These compounds were found to homopolymerize with difficulty to give low molecular weight polymers. Their effect upon the polymerization of methyl methacrylate and styrene was investigated by rate and viscosity measurements. Copolymerizations occurred with a retarding action attributed to pronounced chain transfer reactions.     

Ferrocene compounds. XXXIX.

In the title compound, [Fe(C₅H₅)(C₁₄H₁₃O)], the plane of the heterocyclic ring is almost perpendicular to the plane of the substituted cyclo­penta­dienyl ring, and the heterocyclic ring adopts a half‐chair conformation. The conformation of the nearly parallel cyclo­penta­dienyl (Cp) rings [the dihedral angle between their planes is 2.7 (1)°] is almost halfway between eclipsed and staggered, and the rings are mutually twisted by about 19.4 (2)° (mean value). The mean lengths of the C—C bonds in the substituted and unsubstituted cyclo­penta­dienyl ring are 1.420 (2) and 1.406 (3) Å, respectively, and the Fe—C distances range from 2.029 (2) to 2.051 (2) Å. The phenyl and unsubstituted cyclo­penta­dienyl rings are involved in C—H⃛π interactions, with intermolecular H⃛centroid distances of 2.85 and 3.14 Å for C—H⃛π(Ph), and 2.88 Å for C—H⃛π(Cp). In two of these interactions, the C—H bond points towards one of the ring bonds rather than towards the ring centroid. In the crystal structure, the C—H⃛π interactions connect the mol­ecules into a three‐dimensional framework.     

Cyclometallated compounds. XV.

The title complex, tetra‐μ‐acetato‐O:O′‐bis{[μ‐1,4‐bis(2‐­pyridyl­oxy)­phenyl­ene‐N,C²:N′,C⁶]dipalladium(II)} bis­(tri­chloro­methane) dihydrate, [Pd₄(C₁₆H₁₀N₂O₂)₂(C₂H₃O₂)₄]·2CHCl₃·2H₂O, the product of the reaction of 1,4‐bis(2‐pyridyl­oxy)­benzene with palladium acetate, is shown to be a tetranuclear, rather than a polymeric, species. It crystallizes about a centre of inversion and has two doubly cyclo­palladated ligands bridged by four acetate groups. The cyclo­palladated ligand is far from planar in the complex and has the central benzene rings π‐stacked. The chelate rings exist in shallow boat conformations.     

GPC analysis of model compounds. I. Phenyl- and benzo-substituted aromatic compounds

A series of 36 compounds of known structure was used in a study to elucidate the mechanism of separation of gel-permeation chromatography (GPC). The various molecular dimensions were defined and measured for these compounds. The elution volume for these compounds was determined by GPC under specified and controlled conditions. The relationships between elution volume and molecular dimension were investigated using computer-based statistical analysis for the entire set of compounds and manual simultaneous equations for smaller sets of compounds. It was found that, as increasingly more molecular dimensions are considered, (1) the importance of the maximum molecular dimension A_p′ (the only dimension considered by many investigators) significantly decreases and (2) a significantly better prediction of the elution volume of these compounds could be made.