(Ph3P)2,Co(CO)2Cl和(dppe-P,P)2CO(CO)+的分子轨道研究

本文对(PH3P)2, Co(CO)2Cl和(dppe-P,P)2CO(CO)+(dppe=Ph2CH2CH2PPh2)五配位C2O对称性模型化合物进行了分轨道研究, 结果表明, 钴的3d轨道很少参与成键, 钴的4s, 4P与配体的S,P轨道通过形式上的二电子三中心键和二电子二中心键的相互作用构成五配位, 此外, 还解释了这两种化合物不同稳定性的原因。     

HCo(CO)4及HCo(CO)3(PH3)的电子结构的CNDO计算

用将s电子和p电子分开处理的“CNDO”法,计算了HCo(CO)_4及HCo(CO)_3(PH_3)的电子结构。计算结果关联了许多实验事实。这方法可用于过渡金属络合物的研究。     

Rh2(CO)4(μ-Cl)2和Rh4(μ-CO)3(CO)4的简正振动分析

金属簇合物具有独特的结构和成键方式。本文对铑簇合物的简正振动分析进行了研究。通过红外光谱用石蜡油糊涂KBr和聚乙烯窗口, 在Nicolet 200SXV FT-IR光谱上测定了Rh2(CO)4(μ-Cl)2的构型, 并使用分子振动全分析程序MVTA(Basic语言), 在PC机上进行计算。     

New access to (η(5)-cyclohexadienyl)Mn(CO)3 and cationic (η(6)-arene)Mn(CO)3 complexes by Suzuki-Miyaura reaction

First Suzuki-Miyaura coupling reactions applied to (η(5)-chloro-cyclohexadienyl)Mn(CO)3 complexes are described and lead to the syntheses of (η(5)-aryl-cyclohexadienyl)Mn(CO)3 and of cationic (η(6)-arene)Mn(CO)3 complexes after rearomatization. The structures of two of the new complexes have been investigated by X-ray diffraction study.     

在线反应红外系统ReactIR~(TM)iC10

<正>ReactIRTMiC10是梅特勒―托利多集团2005年推出的第四代实验室在线反应红外分析系统,它采用傅立叶变换红外技术,结合多种CompTM探头构成具有耐化学腐蚀性和机械摩蚀性的系统。ReactIRTMiC10的价值:1)在反应过程中通过CompTM探头直接监测反应过程。2)跟踪反应物、中间物和产物的瞬时变化;跟踪浓度变化,提供反应趋势、终点和各个过程的转化率;测定反应的化学动力学、机理和反应路线。3)优化反应条件(温度、反应时间、压力等)以提高目标产物的产率;了解影响反应的关键过     

Me_3NO存在下Ir_4(CO)_(11)L(L=CO,PPh_3)的CO取代反应动力学研究

刊用FT-IR和UV技术跟踪反应进程,研究了在Me_3NO存在下Ir_4(CO)_(12)和Ir_4(CO)_(11)PPh_3分别在CHCl_3—C_2H_5OH和CHCl_3溶剂中取代羰基反应的动力学与机理。结果表明反应遵循二级速率定律:r=k_2[Me_3NO][配合物]。该速率方程与缔合机理相一致。将Ir_4(CO)_(11)L和Os_3(CO)_(11)L(L=CO,PPh_3)体系的动力学结果相比较,着重讨论了桥基因素对反应活性的影响。     

Carbonylmetall-verbindungen des bis(di-t-butylphosphino)schwefeldiimids: Bildung von zweikernkomplexen S{NPtBu2[MLn]}2 (MLn = Cr(CO)5), Mo(CO)5, W(CO)5, Fe(CO)4) und chelatkomplexen S(NPtBu2)2M(CO)4 (M = Cr,Mo, W). Kristall- und molekülstruktur von S(NPtBu2)2Cr(CO)4

The reaction of bis(di-t-butylphosphino) sulphur diimide, S(NP^tBu₂)₂ (1) ¹, with coordinatively unsaturated 16-electron complex fragments [M(CO)₅] leads to both binuclear 1 : 2 adducts S{NP^tBu₂[M(CO)₅]}₂ (M = Cr (2B), Mo (3B) and W (4B)) and mononuclear chelate complexes S(NP^tBu₂)₂M(CO)₄ (M = Cr (2C), Mo (3C) and W (4C)). A binuclear compound S{NP^tBu₂[Fe(CO)₄]}₂ (5B) is obtained from the reaction of 1 with Fe₂(CO)₉. The new complexes which all contain the intact sulphyr diimide 1 are characterized on the basis of their infrared, ¹H, ¹³C and ³¹P NMR spectra. An X-ray structure analysis of S(NP^tBu₂)₂Cr(CO)₄ (2C) reveals a distorted octahedral coordination sphere around the central chromium atom and an almost planar but twisted six-membered Cr(PN)₂S heterocycle with angles of 91.98(2)° at chromium (P(1)CrP(2)) and 124.6(1)° at sulphur (N(1)SN(2)).     

Phosphine-centred resolution of (η4-diene)Fe(CO)3 complexes: (η4-tropone)Fe(CO)2L and (η4-isoprene)Fe(CO)2L [L = (+)-(neomenthyl)PPh2]

(η⁴-Tropone)Fe(CO)₃ and (η⁴-isoprene)Fe(CO)₃ form separable diastereoisomers on substitution of CO by (+)-(neomenthyl)PPh₂. In the tropone complex, diastereoisomer interconversion occurs by a 1,3-metal shift. The absolute configuration of the isoprene complex has been determined crystallographically.     

对苯二甲酸二丙炔醇酯与C02(CO)8、M02Cp2(CO)4和RuC02(CO)11的反应

室温下,对苯二甲酸二丙炔醇酯分别与Co2(CO)8,Mo2Cp2(CO)4和RuCo2(CO)11反应,得到三个有机金属化合物[C6H4-p-(CO2CH2C2H-μ)2][Co2(CO)6]2(1)、[C6H4-p-(CO2CH2C2H)2][RuCo2(CO)9]2(2)和[(HC2CH2OCO)C6H4-p-(CO2CH2C2H-μ)][Mo2Cp2(CO)4](3).研究发现三种金属核对端炔氢的屏蔽作用依次为RuCo2(CO)9＞Co2(CO)6＞Mo2(CO)4Cp2.化合物1的晶体衍射发现,属三斜晶系,空间群PT,a=8.139(2)A,b=8.808(3)A,c=1 1.343(3)A,β=96.260(6)°,V=773.4(4)A3,Z=1,Dc=1.748g@cm-3,R=0.0513,wR=0.1266.     

Cp*MCpMoFe(CO)7(μ3-S), Cp*MoCpMFe(CO)7(μ3-S) (M = W,Mo) and Cp*WCp*MoFe(CO)7(μ3-S). Crystal structure of CpMoCp*WFe(CO)7(μ3-S)

CpMoFeCo(CO)₇(₃-S) reacts with Cp^*M(CO)₃Cl or CpM(CO)₃Cl (M=W, Mo) to gave the mixed-metal clusters Cp^*WCpMoFe(CO)₇(₃-S) (1), Cp^*MoCpMoFe(CO)₇(₃-S) (2), CpWCp^*MoFe(CO)₇(₃-S) (3), CpMoCp^*MoFe(CO)₇(₃-S) (4) and Cp^*WCp^*MoFe(CO)₇(₃-S) (5). The title clusters have been characterized by i.r., ¹H/¹³C-n.m.r. spectroscopy and their compositions have been confirmed by elemental analyses. The X-ray crystal structure analysis shows the two independent enantiomeric molecules of clusters (1) in one crystal structure unit.     

Electrochemical reductive acylation of (η6-arene)Cr(CO)3 complexes and (benzophenone)[Cr(CO)3]2

The electrochemical reductive acylation of (benzophenone)Cr(CO)₃ and (benzophenone) [Cr(CO)₃]₂ has been performed in DMF, by electrochemical reduction of complexed ketones in the presence of acetic and benzoic anhydride in excess. Three complexed benzhydryl esters ArCH(OCOR)PhCr(CO)₃, (Ar = Ph, R = Me: Ar = PhCr(CO)₃, R = Me; Ar = PhCr(CO)₃, R = Ph) were obtained in 46–57.5% yields after purification. Electrochemical reduction of (diphenylmethane)Cr(CO)₃ in the presence of acetic anhydride in excess leads to m-benzyl acetophenone.     

CO_2(CO)_8-Ru_3(CO)_(12)体系对乙烯氢甲酰化反应的双金属协同效应

本文介绍了Ru_3(CO)_(12)-Co_2(CO)_8混合体系对乙烯氢甲酰化反应的双金属协同效应。实验系用一定量的Co_2(CO)_8和Ru_3(CO)_(12)混合在一起为催化剂体系,以乙烯、合成气(H_2/CO=1)为原料,在110℃,7.6MPa压力下研究了对乙烯氢甲酰化反应的活性,并和相应的Co_2(CO)_8和Ru_3(CO)_(12)的单组分体系作了对比。结果表明Co-Ru双组分体系的活性远高于相应的单组分体系的活性。红外光谱考察表明,Co_2(CO)_8-Ru_3(CO)_(12)在用于烯烃氢甲酰化反应后,Co_2(CO)_8Ru_3(CO)_(12)之间没有因相互作用而产生新化合物。过去对氢甲酰化反应的催化循环,是基于在单一的络合物金属中心上讨论的。基于本文结果,可以设定在双金属体系存在下,烯烃氢甲酰化反应的催化循环有可能在双金属中心上实现。     

AcQ·Tag~(TM)法测定鱼粉水解液中的氨基酸

１前言鱼粉是动物性蛋白质饲料,过去鱼粉中氨基酸测定大多采用氨基酸分析仪以离子交换树酯分离,柱后衍生测定。但氨基酸分析仪价格昂贵,分析时间长。近年来,柱前衍生高效液相色谱法测定氨基酸的技术因其具有衍生步骤简单,速度快,剩余试剂不干扰测定等优点,而有逐渐...     

(μ-RS)(μ-XMgS)Fe2(CO)6亲核性能的研究:铁硫配合物(μ-RS)[μ-Cp(CO)2FeS]Fe2(CO)6

研究了(μ-RS)(μ-XMgS)Fe2(CO)6与π-环戊二烯二羰基碘化铁的反应.首次制得(μ-RS)[(μ-CpFe(CO)2S]Fe2(CO)6的一系列含有机铁硫桥的非对称配合物.它们的核磁氢谱表明每个络合物只是以一类构象体存在.它们的甲基络合物的单晶结构分析证实了这一结论.     

Evolved gas analysis–ion attachment mass spectrometric observation of Mn(CO)5 and Mn2(CO)9 radicals produced by Mn2(CO)10 pyrolysis

Evolved gas analysis?Cion-attachment mass spectrometry (EGA?CIAMS) indicates that Mn(CO)₅ and Mn₂(CO)₉ free radicals are produced in the gas phase by pyrolysis of Mn₂(CO)₁₀ in an infrared image furnace. The Li⁺-adduct mass spectra of the pyrolysis products contained peaks at m/z 202 and 369 for Mn(CO)₅Li⁺ and Mn₂(CO)₉Li⁺, respectively, providing direct evidence that d-metal complex radicals were formed in the furnace. We studied the effect of temperature on the rate of production of the radicals, and confirmed the presence of the compounds Mn(CO)₅ and Mn₂(CO)₉, which were reported in earlier studies based on electron-impact mass spectrometry, electron spin resonance spectroscopy, and Fourier transform infrared spectroscopy.     

Hydrogen adsorption on C3H3–TM (TM = Sc, Ti) organometallic compounds

This work reports hydrogen adsorption on C₃H₃–TM (TM = Sc, Ti) organometallic compounds using second-order Møller–Plesset perturbation theory method. Two types of organometallic compounds are considered viz. transition metal-capped and transition metal-inserted. Maximum five and four hydrogen molecules were adsorbed on Sc-capped ScC₃H₃ and Ti-capped TiC₃H₃ complexes, thereby giving gravimetric hydrogen uptake capacity of 10.71 and 8.5 wt%, respectively. The gravimetric H₂ uptake capacity 10.71 wt% of ScC₃H₃ complex is higher by 1.41 wt% than that of Sc-capped ScC₄H₄ organometallic complex reported earlier. The hydrogen uptake capacity 8.5 wt% of TiC₃H₃ is in between the uptake capacity of 6.61 and 9.1 wt% shown by Ti-capped TiC₅H₅ and TiC₄H₄ organometallic complexes, respectively. The Sc-capped and Sc-inserted ScC₃H₃ adsorb same number of H₂ molecules whereas Ti-inserted TiC₃H₃ complex adsorbs less number of H₂ molecules than that of Ti-capped TiC₃H₃ complex. Nature of interactions between different molecules in hydrogen-adsorbed complexes is studied. The binding energy per H₂ molecules differ by about 0.1 eV in transition metal-capped and transition metal-inserted structures.     

(μ3-S)FeCo2(CO)7(dppfe)的合成和晶体结构

通过简单取代反应,合成了一个新的混金属簇合物(μ3-S)FeCo2(CO)7(dppfe) (2) (dppfe=Ph2PC5H4FeC5H4PPh2).利用IR,1H NMR,MS 和 X-ray单晶衍射的方法对簇合物2进行了结构表征.簇合物2的晶体属于三斜晶系,空间群为Pī.晶胞参数: a=1.132 4(15) nm, b=1.3670(17) nm, c=1.5769(2) nm,α=114.646(2)°,β=100.340(2)°,γ=100.113(3)°, V=2.0953(5) nm3.