Syntheses and Crystal Structures of Two New Iron-sulfur Carbonyl Complexes: [Fe_2(SC_6H_4Cl)_2(CO)_6]·0.5(Et_2O) and [Fe_3(SC_6H_4NH_2)_6(CO)_6]·2(MeOH)

Two new iron-sulfur carbonyl complexes, [Fe2（SC6H4Cl）2（CO）6]·0.5（Et2O） 1 and [Fe3（SC6H4NH2）6（CO）6]·2（MeOH） 2, have been prepared and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. Crystal data for 1： monoclinic, C2/c, a = 18.4439（8）, b = 11.0999（5）, c = 25.1830（10）A°, β = 97.0370（10）°, V = 5116.8（4） A°^3, Z = 8, C20H13Cl2Fe2O6.50S2, Mr = 604.02, Dc = 1.568 g/cm^3, μ = 1.540 mm^-1, F（000） = 2424, the final R = 0.0545 and wR = 0.1454 for 3443 observed reflections with I 〉 2σ（I）; 2： monoclinic, P21/n, a = 12.350, b = 26.3050（11）, c = 16.057A°, β = 97.891 （3）°, V = 5166.9（2）A°^3, Z = 4, C44H44Fe3N6O8S6, Mr = 1144.76, Dc = 1.472 g/cm^3, μ = 1.128 mm^-1, F（000） = 2352, the final R = 0.0442 and wR = 0.1197 for 7978 observed reflections with I 〉 2σ（I）. Complex 1 contains one iron dimer, in which two tricarbonyliron（Ⅰ） fragments are bridged together by two 4-chlorophenylthiolate ligands, whereas complex 2 contains a linear tri-iron cluster, in which two terminal tricarbonyliron（Ⅱ） fragments and the central Fe（Ⅱ） atom are linked together by six 4-aminophenylthiolate bridging ligands.

Mononuclear Carbonyl Anion Complexes of GroupsⅣandⅤMetals

The anionic carbonyl complexes of groupsⅣandⅤmetals TM(CO)6,7(TM=Ti,Zr,Hf,V,Nb,Ta)are prepared in the gas phase using a laser vaporation-supersonic expansion ion source.The infrared spectra of TM(CO)_(6,7)-anion complexes in the carbonyl stretching frequency region are measured by mass-selected infrared photodissociation spectroscopy.The six-coordinated TM(CO)_(6)-anions are determined to be the coordination saturate complexes for both the groupⅣand groupⅤmetals.The TM(CO)_(6)-complexes of groupⅣmetals(TM=Ti,Zr,Hf)are 17-electron complexes having a~2A1gground state with D3dsymmetry,while the TM(CO)_(6)-complexes of groupⅤmetals(TM=Ⅴ,Nb,Ta)are 18-electron species with a closed-shell singlet ground state possessing Ohsymmetry.The energy decomposition analyses indicate that the metal-CO covalent bonding is dominated by TM-(d)→(CO)6π-backdonation and TM-(d)←(CO)6σ-donation interactions.

Influence of shape anisotropy on microwave complex permeability in carbonyl iron flakes/epoxy resin composites

To explore the mechanism of carbonyl iron flake composites for microwave complex permeability, this paper investigates the feature of the flakes. The shape anisotropy was certified by the results of the magnetization hysteresis loops and the Mossbauer spectra. Furthermore, the shape anisotropy was used to explain the origin of composite microwave performance, and the calculated results agree with the experiment. It is believed that the shape anisotropy dominates microwave complex permeability, and the natural resonance plays main role in flake.

A Novel Synthesis of Dimethyl Malonate by Carbonylation of Methyl Chloroacetate Catalyzed by Cobalt Complex

A novel method of preparing dimethyl malonate by carbonylation of methyl chloroacetate catalyzed by Na[Co(CO)(4)] was proposed. Na[Co(CO)(4)] was synthesized in situ in the presence of Na2S2O3 and iron powder. The effects of some reaction parameters such as temperature. CO pressure and the concentrations of catalyst on the yields of dimethyl malonate were discussed. The kinetic data were studied and a possible reaction mechanism was proposed.

Reactivity of Fe3(CO)(12) with Alkynes R-C≡C-R＇： Syntheses and Crystal Structures of Substituted Cyclic Ketones and Carbonyl Iron Complexes

The reactivity of carbonyl iron cluster with alkynes has been studied by the thermal reaction of Fe_3（CO）_（12） with R-C≡C-R＇（R = Fc（Ferrocenyl）; R′ = Ph（Phenyl）, Fc, H）. The hexacarbonyldiiron cluster with ferracyclopentadiene ring（μ_2, η~4-C_4Ph_4）Fe_2（CO）_6（1） and one tetraphenyl substituted cyclopentadienone（Ph_4C_4CO）（2） were simultaneously obtained by the reaction of Fe_3（CO）_（12） with alkyne（Ph-C≡C-Ph）. Only one ferrole cluster（μ_2, η~4-C_4Fc_2H_2）Fe_2（CO）_6（3） was separated by using Fc-C≡C-H as alkyne. One tri-carbonyl iron complex（η~4-C_4Fc_4CO）Fe（CO）_3（4） and an unexpected new cyclic ketone compound 2,2,4,5-tetraferrocenylcyclopenta-4-en-1,3-di-one [Fc_4C_3（CO）_2]（5） were obtained by using Fc-C≡C-Fc as alkyne. A new complex（η4-2,4-diphenyl-3,5-diferrocenylcyclopenta-2,4-dien-1-one）-tricarbonyl iron（η~4-C_4Ph_2Fc_2CO）Fe（CO）_3（6） was synthesized by the reaction of Fe_3（CO）_（12） with Fc-C≡C-Ph. The structures of compounds 1~6 were determined by X-ray single-crystal diffraction and spectroscopic characterization. The crystal structures of two new compounds 5 and 6 were analyzed. Our experimental results reveal the structural models of the reaction products are affected by the kinds of substituents from alkynes R-C≡C-R′.

STUDY OF CARBONYLATION OF METHANOL TO ACETIC ACID AND ACETIC ANHYDRIDE OVER A BIDENTATE POLYMER BOUND CIS-DICARBONYLRHODIUM COMPLEX AS CATALYST

Copolymer of 2-vinylpyridine and vinylacetate coordinated with dicarbonylrhodium used as a catalyst for carbonylation of methanol to acetic acid and anhydride has been studied. The structural characteristics of the copolymer ligand and complex, and the influences of the reaction conditions on the carbonylation catalyzed by this polymer complex have been investigated. In comparison with small molecule catalyst of Rh complex, the bidentate copolymer coordinated complex has better thermal stability. The reaction mechanism of the carbonylation reaction is also illustrated.

Carbonylative Coupling of 4,4’-Diiodobiphenyl Catalyzed by Pd(NHC) Complex

To develop a luminescent material with high color purity, luminous efficiency, and stability, we synthesized diketone by carbonylative Suzuki coupling in the presence of Pd(NHC) complex as the catalyst. Carbonylative coupling of 4,4’-diiodobiphenyl and phenylboronic acid was investigated to study in detail the catalytic ability of the Pd(NHC) complex. Reactions were carried out using both CO and metal carbonyls. Bis-(1,3-dihydro-1,3-dimethyl-2H-imidazol- 2-ylidene) diiodo palladium was used as the catalytic complex. Reaction products biphenyl-4,4’-diylbis (phenyl- methanone) 3 and (4’-iodobiphenyl-4-yl)(phenyl) methanone 4 were obtained as a result of CO insertion into the palladium(II)-aryl bond. However, when pyridine-4-yl boronic acid was used in place of phenylboronic acid as the starting reagent, synthetic reaction yielding 3 and 4 were found not to occur.

A NOVEL COPOLYMER-BOUND CIS-DICARBONYLRHODIUM COMPLEX FOR THE CARBONYLATION OF METHANOL TO ACETIC ACID AND ACETIC ANHYDRIDE

A series of porous microspheres of linear and ethylene diacrylate (M') cross-linked copolymers of 2-vinylpyridine (V) and methyl acrylate (M) reacted with tetracarbonyldichlorodirhodium to form a series of cis-dicarbonylrhodium chelate complex (MVRh and MVM 'Rh). They are thermally stable yet very reactive in the carbonylation of methanol to acetic acid, and of methanol-acetic acid mixture to acetic acid and acetic anhydride with a selectivity of 100% under relatively mild and anhydrous conditions.

KINETIC STUDY OF CARBONYLATION OF METHANOL TO ACETIC ACID AND ACETIC ANHYDRIDE OVER A NOVEL COPOLYMER-BOUND CIS-DICARBONYLRHODIUM COMPLEX

The kinetic study of carbonylation of methanol-acetic acid mixture to acetic acid and acetic anhydride over a cis-dicarbonylrhodium complex (MVM' Rh) coordinated with the ethylene diacrylate (M') crosslinked copolymer of methyl acrylate (M) and 2-vinylpyddine (V)shows that the rate of reaction is zero order with respect to both reactants methanol and carbon monoxide, but first order in the concentrations of promoter methyl iodide and rhodium in the complex. Polar solvents can accelerate the reaction. Activation parameters were calculated from the experimental results, being comparable to that of the homogeneous system. A mechanism similar to that of soluble rhodium catalyst was proposed.

The Activation and Carbonylation of the C-Cl Bond Catalyzed by Transition-Metal Complexes

Diethyl malonate was synthesized by transition-metal catalyzed alkoxycarbonylation of ethyl chloroacetate. The results show that the conversion of ethyl chloroacetate is greater than 92%, and the selectivity to diethyl malonate is 67.5%.

Infrared Spectra,Structures and Bonding of Binuclear Transition Metal Carbonyl Cluster Ions

Binuclear transition metal carbonyl clusters serve as the simplest models in understand- ing metal-metal and ligand bonding that are important organometallic chemistry catalysis. Binuclear first row transition metal carbonyl ions are produced via a pulsed laser vaporiza- tion/supersonic expansion cluster ion source in the gas phase. These ions are studied by mass-selected infrared photodissociation spectroscopy in the carbonyl stretching frequency region. Density functional theory calculations have been performed on the geometric struc- tures and vibrational spectra of the carbonyl ions. Their geometric and electronic structures are determined by comparison of the experimental IR spectra with the simulated spectra. The structure and the metM-metal and metal-CO bonding of both saturated and unsaturated homonuclear as well as heteronuclear carbonyl cluster cations and anions are discussed.

Removal of carbonyl sulfide from CO_2 stream using AgNO_3-modified NaZSM-5

Removal of carbonyl sulfide(COS) from CO2 stream is significant for the production and utilization of food grade CO2. This study investigates the adsorption performance of Ag/NaZSM-5 as adsorbent prepared by incipient wetness impregnation for the removal of COS from a CO2 stream in a fixed-bed adsorption apparatus. Effects of various conditions on the preparation of adsorbent, adsorption and desorption were intensively examined. The results revealed that COS can be removed to below 1×10-9from a CO2stream(1000 ppm COS/CO2) using Ag/NaZSM-5(10 wt% AgNO3) with an adsorption capacity of 12.86 mg·g-1. The adsorbent can be fully regenerated using hot air at 450 C. The adsorption ability remained stable even after eight cycles of regeneration.

Cobalt-catalyzed photopromoted carbonylation of chloroalkanes in the presence of KI

The photopromoted carbonylation of chloroalkanes with carbon monoxide catalyzed by cobalt compounds[Co（OAc）2,CoCl2] in the presence of KI was carried out under ambient conditions.The results revealed that the catalytic activity of Co（OAc）2 was higher than that of CoCl2.A basic additive NaOAc was beneficial to the reaction.Interestingly,with NaOAc as an additive, Co（OAc）2 and CoCl2 exhibited similar catalytic activity.Preliminary work showed that the role of iodide ion was initially to form active iodoalkanes via substituting chloride ion in chloroalkanes in situ,and then,the carbonylation of iodoalkanes proceeded under irradiation.

羰基合成与羰基化催化剂的研究进展及工业化应用

羰基合成反应在催化化学中扮演着重要角色,并通过新合成方法和新物质的多样性创制成为生产多种含氧化合物及高附加值产品的重要途径。而恰当的催化体系是羰基合成工艺和技术的关键,也是羰基化反应实现工业化的研究重点。首先从不同的反应底物、不同的羰基来源以及不同的反应类型等方面对羰基合成反应及研究进展进行概述,然后从以金属和非金属为活性中心的角度对羰基化催化剂的应用及研究进展进行阐述,最后列举了几种典型的羰基合成反应及羰基化催化剂在工业上的应用。

非均相催化一步合成碳酸二苯酯的研究 Ⅳ.活性组分及其负载方法对催化剂性能的影响

采用浸渍法、沉淀法、混烧法和溶胶 凝胶法制备了非均相催化一步合成碳酸二苯酯 (DPC)所需的催化剂 ,对活性组分不同负载方法所得催化剂的比表面积和形貌进行了观测 ,并通过DPC合成实验评价了催化剂的催化性能 .结果表明 ,沉淀法所得催化剂的形貌及催化性能都比较好 .为了进一步寻找制备催化剂的适宜条件 ,就沉淀法所用的沉淀剂、活性物质及助剂对催化剂性能的影响进行了探讨 .结果表明 ,以NaOH为沉淀剂 ,以Na2 PdCl4 为活性物质 ,以Sn为助活性组分 ,其效果较好 ,DPC的选择性和收率分别可达 93%和 7 2 % .此外 。

配合物[(C3H7)4N]2Cu2Br6的制备及其对甲醇氧化羰化反应的催化性能

A bromine-containing copper-organic coordination compound was prepared by the reaction of tetrrpropylammonium bromide with copper bromide in ethyl acetate solution.The compound obtained was characterized with FTIR,XRD,ICP-AES and EA.Meanwhile,its catalytic performance for the oxidative carbonylation of methanol was investigated.The results showed that the introduction of ligand could change the density of copper electron cloud,which improved the redox property for the oxidative carbonylation of methanol to prepare dimethyl carbonate.In the presence of strong base and weak acid salts,the per pass conversion of methanol could reach 57% under the reaction conditions of temperature 383 K,pressure 3.5 MPa,and the mass concentration of catalyst in methanol 0.20 g·ml-1.

一种新的潜在心肌显像剂[^(99m)Tc(CO)_3(TBI)_3]^+的制备及其生物分布研究

以 [99m Tc O4]- 为起始物 ,在 0 .1 MPa下制备了中间体 [99m Tc( CO) 3 ( H2 O) 3 ]+,通过配体交换反应 ,叔丁基异腈 ( TBI)配体取代该配合物中的 3个水分子 ,制得一种标记率大于 90 %的 [99m Tc( CO) 3 ( TBI) 3 ]+配合物 .该配合物在室温下放置 6 h以上 ,标记率无明显变化 .在正常昆明小鼠体内的生物分布实验结果表明 ,[99m Tc( CO) 3 ( TBI) 3 ]+具有较高的心肌摄取 ,且滞留也相当好 ,在静脉注射 5 min和 6 0 min后时的心肌摄取值分别为 ( 1 9.0 7± 0 .81 ) % ( ID/g)和 ( 1 8.2 4± 2 .4 1 ) % ( ID/g) .该配合物的非靶本底摄取较低 ,注射 6 0 min后的心 /肝、心 /肺和心 /血摄取比值分别为 1 .0 2 ,5 .83和 2 3.6 9,有望发展为一种新的心肌显像剂 .

芳基取代四甲基环戊二烯基铼羰基化合物的合成、晶体结构及催化性能（英文）

芳基取代的四甲基环戊二烯C5HMe4Ar(Ar=Ph,4-CH_3Ph,4-OCH_3Ph,4-ClPh,4-BrPh)分别与Re2(CO)10在二甲苯中加热回流,得到了5个单核配合物[(η5-C5Me4Ar)Re(CO)3](Ar=Ph(1),4-CH_3Ph(2),4-OCH_3Ph(3),4-ClPh(4),4-BrPh(5))。通过元素分析、红外光谱、核磁共振氢谱对配合物1~5的结构进行了表征,用X射线单晶衍射法测定了配合物的结构。同时,研究了这五种配合物在芳香族化合物Friedel-Crafts烷基化反应中的催化活性。

4-乙烯吡啶-丁烯酮共聚物与铑的顺二羰基配合物结构和性能研究

在铑催化剂的作用下,甲醇与一氧化碳经羰基化反应为乙酸和乙酸甲酯,是60年代发展起来的新工艺,但以往多是采用均相小分子铑催化剂,除我们的工作以外,迄今尚少见报道有采用以共聚物为配体的高分子铑催化剂的成功先例。