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Muthiah Senthil Kumar 《Journal of organometallic chemistry》2006,691(22):4708-4716
Reactions of [η5-carboxycyclopentadienyl][η4-tetraphenylcyclobutadiene] cobalt, Ph4C4CoC5H4COOH (1), with (Ph3Sn)2O, [(n-Bu)2SnO]n and (Ph2SnO)n in refluxing toluene resulted in the formation of the monomeric compound Ph3SnOC(O)C5H4CoC4Ph4 (2) and dimeric compounds n-Bu2Sn[OC(O)C5H4CoC4Ph4]2 (3) and Ph2Sn[OC(O)C5H4CoC4Ph4]2 (4), respectively. Reactions carried out in the solid state by mechanical grinding also yielded same results. Crystal structure determination and cyclic voltammetric studies of compounds 1, 2, 3 and 4 have been carried out and compared with similar ferrocene carboxylic acid derivatives. The structures and electrochemistry of these compounds are compared with analogous organotin ferrocene carboxylates. The results obtained from the reaction of 1 with alkyl and aryl tin oxides suggest that the formation of stannoxanes assemblies having more than two carboxylate units are not favored indicating that 1 is a highly sterically hindered metallocene carboxylic acid. 相似文献
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《Journal of organometallic chemistry》1991,412(3):C37-C39
Single addition of the nucleophiles X− (X = H, CN, OH) to the less sterically hindered ring in [(η6-C6Me6)Ru(η6-C16H16)][BF4]2 (1) proceeds smoothly to produce, as the sole product, [(exo-η5-C6Me6X)Ru(η6-C16H16)][BF4]. Use of Na[BD4] in place of Na[BH4] gives the expected shift in ν(C-Hexo) in the infrared spectrum. 相似文献
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以2-苯氧乙基为氮支链的[18]和[15]环系氮支套索冠醚的合成及其络合性能 总被引:1,自引:0,他引:1
以2-苯氧乙醇为起始剂, 合成了两种新型氮支套索冠醚: N-(2-苯氧乙基)单氮杂-18-冠-6 (18CE)与N-(2-苯氧乙基)单氮杂-15-冠-5 (15CE). 通过红外光谱、核磁共振氢谱和紫外光谱表征了新冠醚及其中间体的结构. 用电导滴定法研究了两冠醚与Na+, K+, Ag+, NH4+, Ni2+, Cu2+, Pb2+和Co2+在25 ℃的配位作用, 计算了1∶1配合物的稳定常数. 实验结果表明, 由于N-(2-苯氧乙基)引入氮杂冠醚环和参与配位, 18CE和15CE配合物的稳定常数分别比单氮杂-18-冠-6, N-(2-羟基乙基)单氮杂-18-冠-6, N-(2-甲氧基乙基)单氮杂-18-冠-6和单氮杂-15-冠-5, N-(2-甲氧乙基)单氮杂-15-冠-5, N-(2-甲氧乙基)单氮杂-15-冠-5的对应配合物明显提高. 配合物的稳定常数和紫外光谱皆提供了支链的苯氧基参与配位的信息. 相似文献
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Deqiang Wang Dr. Wanjian Ding Dr. Guohua Hou Prof. Guofu Zi Prof. Dr. Marc D. Walter 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(22):6767-6782
The synthesis, electronic structure, and reactivity of a uranium metallacyclopropene were comprehensively studied. Addition of diphenylacetylene (PhC≡CPh) to the uranium phosphinidene metallocene [η5-1,2,4-(Me3C)3C5H2]2U=P-2,4,6-tBu3C6H2 ( 1 ) yields the stable uranium metallacyclopropene, [η5-1,2,4-(Me3C)3C5H2]2U[η2-C2Ph2] ( 2 ). Based on density functional theory (DFT) results the 5f orbital contributions to the bonding within the metallacyclopropene U-(η2-C=C) moiety increases significantly compared to the related ThIV compound [η5-1,2,4-(Me3C)3C5H2]2Th[η2-C2Ph2], which also results in more covalent bonds between the [η5-1,2,4-(Me3C)3C5H2]2U2+ and [η2-C2Ph2]2− fragments. Although the thorium and uranium complexes are structurally closely related, different reaction patterns are therefore observed. For example, 2 reacts as a masked synthon for the low-valent uranium(II) metallocene [η5-1,2,4-(Me3C)3C5H2]2UII when reacted with Ph2E2 (E=S, Se), alkynes and a variety of hetero-unsaturated molecules such as imines, ketazine, bipy, nitriles, organic azides, and azo derivatives. In contrast, five-membered metallaheterocycles are accessible when 2 is treated with isothiocyanate, aldehydes, and ketones. 相似文献
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本文通过η^5-Bz~5C~5MNa与氧化偶联试剂Fe~2(SO~4)~3/HOAC/H~2O的反应合成了含η^5-五苄基环戊二烯基配体的两个金属-金属单键化合物[η^5-Bz~5C~5(CO)~3M]~2 (1: M=Mo; 2: M=W) , 产率分别为45%和19% . 1 在沸腾的甲苯中可进一步脱碳而以98%的产率生成金属-金属叁键化合物[η^5-Bz~5C~5(CO)~2Mo]~2 (3).1~3的结构均经碳氢分析, IR, ^1H NMR 和MS鉴定. 3的结构尚被单晶X射线衍射分析确证 . 相似文献
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铁液中[Ce]-[O]-[S]沉淀图及其应用 总被引:1,自引:0,他引:1
选用近期实验所测较为准确的稀土-氧、稀土-硫、稀土-氧-硫体系的热力学数据建立了纯铁液中的[Ce]-[O]-[S]空间沉淀图。应用热力学理论计算了铁液中氧硫活度与生成的稀土夹杂物间的定量关系。确定了铁水初始氧硫活度与生成稀土夹杂物类型的关系,并验证了理论计算结果。 相似文献
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Russian Journal of Organic Chemistry - New spiro heterocycles, spiro[benzo[h]chromene-4,3′-indoles] and spiro[benzo[f]chromene-1,3′-indoles], have been synthesized in 50–60% yield... 相似文献
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《Polyhedron》1999,18(21):2737-2747
Nucleophilic substitution reactions of various acetylides on substituted tricarbonyl(η6-fluoroarene)chromiums were pursued. The reaction presumably underwent a more complicated mechanism rather than the direct substitution on the fluorine-bearing carbon. The organometallic compounds (η6-C6H3R1R2R3)Cr(CO)3 (R1: CC–C6H4CH3, R2: o-Me, R3: H (5a), R1: CC–C6H4CH3, R2: o-OMe, R3: H (6a), R1: CC–C6H4CH3, R2: m-OMe, R3: H (6b), R1: CCPh, R2: o-Me, R3: o-OMe (8b), R1: CCPh, R2: m-Me, R3: m-OMe (8c), R1: CCSiMe3, R2: o-Me, R3: H (9a), R1: CC–C6H4CCH, R2: H, R3: H (12), R1: CC–C6H4CCH, R2: o-Me, R3: H (13)) as well as the organometallic dimmer [{(η6-o-Me-C6H4)Cr(CO)3(di-ethynyl)] (di-ethynyl: CC–C6H4CC (14)) have been synthesized from nucleophilic substitution reactions of tricarbonyl(η6-fluoroarene)(chromium) compounds with suitable acetylides. The products have been characterized by spectroscopic means. In addition, (8b) and (8c) were characterized by X-ray diffraction studies. Further reactions of (9a) and (12) with appropriate amount of Co2(CO)8 yielded μ-alkyne bridged bimetallic complexes, Co2(CO)6{μ-Me3SiCC–(o-tolueneCr(CO)3} (10) and (Co2(CO)6)2{μ-HCC–C6H4–CC–(benzene)Cr(CO)3)}(15), respectively. Both (10) and (15) were characterized by spectroscopic means as well as single crystal X-ray crystallography. The core of these molecules is quasi-tetrahedron containing a Co2C2 unit. A two-dicobalt-fragments coordinated di-enyls complex, (Co2(CO)6)2{μ-HCC–C6H4–CC–H} (17), was synthesized from the reaction of 1,3-diethynylbenzene with Co2(CO)8. Crystallographic studies of (17) also show that it exhibits a distorted Co2C2 quasi-tetrahedral geometry. 相似文献
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One linear template 13 and one cyclophane template 15, both incorporating two electron rich 1,4‐dialkoxybenzene units and one diamide unit, have been synthesized. By utilizing donor‐acceptor interaction and/or intermolecular hydrogen bonding assembling principles, one novel hetero[3]rotazane 22·4Cl, possessing one neutral and one tetracationic ring components, has been synthesized from 13, through neutral [2]rotaxane 21 as intermediate. With 15 as template, tetracationic [2]catenane 23·4PF6 was assembled by using donor‐acceptor interaction, but no neutral [2]rotaxane could be obtained under the typical conditions of hydrogen bonding assembling principle. The interlocked supramolecular compounds have been characterized and their spectral properties are investigated. 相似文献
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A. I. Yanovsky F. M. Dolgushin Yu. T. Struchkov V. S. KaganovicH M. I. Rybinskaya 《Russian Chemical Bulletin》1995,44(6):1072-1079
It has been established by X-ray structural study that the bicluster cobalt -arene complex of diphenylmethane [6-PhCo4CO9]2CH2 and binuclear complex [6-PhCr(CO)3]2CH2 have ans-trans-s-trans conformation in their crystals.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1111–1117, June, 1995.This work was supported by the Russian Foundation for Basic Research (Projects No. 93-03-4028 and 94-03-08338). 相似文献
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We studied characteristics of [2] or [3]pseudorotaxanes based on stilbene dye SD?CB[7] . In neutral or weak alkaline conditions, SD could be encapsulated inside the stilbene site of CB[7] with 1:1 stoichiometry, whereas, with the pH changing to acidity, the hydrogen bonding between the carboxyl group and the carbonyl of CB[7] maked another CB[7] molecule include into hexanoic acid site, these processes were confirmed by fluorescence spectra,UV–Vis spectra and 1H NMR. 相似文献
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本文通过η~5-Bz_5C_5MNa与氧化偶联试剂Fe_2(SO_4)_3/HOAc/H_2O的反应合成了含η~5-五苄基环戊二烯基配体的两个金属-金属单键化合物[η~5-Bz_5C_5(CO)_3M]_2(1:M=Mo;2:M=W),产率分别为45%和19%。1在沸腾的甲苯中可进一步脱羰而以98%的产率生成金属-金属三键化合物[η~5-Bz_5C_5(CO)_2Mo]_2(3)。1~3的结构均经碳氢分析,IR,~1H NMR和MS鉴定。3的结构尚被单晶X射线衍射分析确证。该晶体属单斜晶系,空间群P2_1/c,晶体学数据:。α=1.1335(5),b=1.3823(4),c=2.1655(6)nm;β=102.33(3)°;V=3.315(2)nm~3;Z=2;D_x=1.34g/cm~3;F(000)=1380。 相似文献
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Qing Qing Meng He Xiang Bai Feng Li Quan Rui Wang Feng Gang Tao 《中国化学快报》2007,18(7):785-787
A convenient synthetic pathway to 2-aryl-5,6-dihydro-4H-benzo[f][1,2,4]triazolo[1,5-α]azepine derivatives 7 was developed. The synthesis was based on the cycloaddition of the 1,2,3,4-tetrahydronaphthalene a-acetoxy azo compounds 3 with Ar-CN in the presence of AlCl3 and the consecutive ring enlargement. 相似文献