Reactions of (η6-Arene)tricarbonylchromium Complexes: Hydrogenation,Nitration, and Bromination

In this study, we explore the reactions of coordinated arenes, e.g., hydrogenation, nitration, and bromination, to prepare compounds which are not accessible from conventional organic synthesis. The reaction products formed from reactions with the coordinated and the uncoordinated arenes are compared. The polycyclic aromatic hydrocarbons (PAHs) employed for this study include phenanthrene, methyl- and acetyl-phenanthrene, and benz[a]anthracene (BA), The tricarbonylchromium group demonstrated various characteristics which influence the reactions in this work, such as an electronic effect to deactivate hydrogenation, a steric effect to exhibit, highly positional selective nitration, and a free radical mechanism to direct bromine to attack at the ring coordinated to tricarbonylchromium.     

A New Hydroxo‐bridged Chromium(III) Dimer [Cr(saltn)OH]2·4H2O: Synthesis,Crystal Structure and Magnetic Properties

A new hydroxo‐bridged dimeric Cr(III) complex [Cr(saltn)OH]₂·4H₂O [H₂saltn=N,N′‐bis(salicylidene)trimethylenediamine] has been synthesized and its structural and magnetic properties have been investigated. The complex crystallizes in the triclinic space group P‐1 with one dimeric formula unit in a cell of dimensions a=0.95828(19) nm, b=0.95926(19) nm, c=1.0437(2) nm, α=86.77(3)°, β=82.48(3)°, and γ=64.93(3)°. The geometry around each chromium(III) center is six‐coordinate, distorted‐octahedral. The bridging Cr₂O₂ unit is strictly planar, as required by the crystallographic symmetry. The Cr? O? Cr′ bridging angle is 99.94(16)°, and the distance between Cr…Cr′ is 0.3019 nm. The magnetic susceptibility of the complex has been examined in the range of 2‐300 K. By using the spin‐spin coupled model for an S₁=S₂=3/2 dimeric system , the magnetic data were fitted to give the parameters of g=2.01(1), J=‐0.85(2) cm^‐1, and zJ' =0.18(3)cm^‐1, indicating the presence of a weak antiferromagnetic spin‐exchange interaction between the Cr(III) ions in the binuclear complex.     

Cr(VI)在Mg-Al型类水滑石上的吸附-脱附性研究I.吸附性

研究了Cr(VI)在带结构正电荷的Mg-Al型类水滑石(HTlc)上的吸附性能,考察了pH、无机电解质添加剂NaCl,NaNO3,Na2SO4和Na3PO4及有机添加剂EDTA和柠檬酸等因素的影响,并结合红外光谱和XRD实验结果探讨了吸附机理.研究表明,Mg-Al型HTlc对Cr(VI)有很强的吸附能力,其吸附动力学和吸附等温线分别符合准二级速率方程和Langmuir方程,饱和吸附量达105mg/g,有望成为一种优良的含Cr(VI)污水处理剂和Cr(VI)污染土壤修复剂.初始pH增大,吸附量降低.无机电解质和有机添加剂均能明显抑制Cr(VI)在HTlc上的吸附,其抑制吸附作用的强弱顺序分别为Na3PO4≥Na2SO4≥NaCl>>NaNO3和柠檬酸>EDTA.Cr(VI)在HTlc上的吸附可分为层间的离子交换吸附和外表面的吸附,其中外表面的吸附层在微观上又可分为因化学键合作用而形成的内络合层和因静电作用而形成的外络合层.     

M_nP_m~+原子簇结构的ab initio从头算(M=Cr,Mn,n=1～3,m=2～12)

应用ahinitio计算程序，我们对飞行时间质谱产生的谱图进行了理论分析。稳定的MnnPm+和CrnPm+的结构基本上是多面体，仅有少数结构为环状和平面的。在计算中，我们尚未发现有链状的簇合物，这与风簇绝大多数是多面体是相一致的。因此，单枚金属簇合物的形成机制很大可能是金属进入磷形成的笼簇中。一般地说，除了磷的个别笼状团簇外，金属和磷相互成键是普遍存在的；在二核、多核金属磷簇合物中，金属间相互作用不常见，绝大多数是通过桥磷相连的。     

钢铁及其合金中铬含量测定结果的不确定度评定

对用GB／T223、11—1991《过硫酸铵氧化容量法测定铬量》的方法测定钢铁及合金中铬含量测量结果的不确定度进行了评定。对样品测量过程中的不确定度分量进行了分析和量化，求得铬含量测定结果的标准不确定度和扩展不确定度分别为0．06％和0．12％。     

火焰原子吸收法测定化妆品中的铬

采用火焰原子吸收分光光度法测定了兰州市的一些市售化妆品中铬的含量。结果表明,方法检测限(3σ)为0.003 mg/L,回收率在94%~105%之间,相对标准差小于1.3%,方法简便快速;市售多数化妆品中的铬含量超过国家标准,须引起人们的注意。     

The complete multi-ζ electric dipole moment matrix of π-(C6H6) Cr(CO)3 and tests of semi-empirical MO models

First, we evaluated the complete electric dipole moment matrixeZ using a multi- AO basis on Cr, C, and O centers fortheimportant, parent organometallic molecule -C₆H₆Cr(CO)₃. Second, we generated ground state LCAO-MO eigenvectors employing five commonly used semi-empirical procedures for molecules of this size which contain transition metals. Transformation of operator matrixeZ into the MO space of each of the five methods then leads us to conclude that the empirical input of Basch, Viste and Gray is most suitable. Finally, we compare the merits of several single- basis orbitals with the multi- metal orbitals.[/p]     

Halbsandwichkomplex des Chroms mit dem Trifluormethylisocyanid-Liganden

Halfsandwich Complexes of Chromium with the Trifluoromethyl Isocyanide Ligand The synthesis and properties of the halfsandwich complexes [η⁶-1,3,5-C₆H₃(CH₃)₃]Cr(CO)₂(CNCF₃), [η⁶-1,3,5-C₆H₃(CH₃)₃]Cr(CO)(CNCH₃)(CNCF₃) und [η⁶-1,3,5-C₆H₃(CH₃)₃]Cr(CNCF₃)₃ is reported. The vibrational spectroscopic data proof the strong π accepting character of the trifluoromethyl isocyanide ligand.     

Solid-state mechanochemical synthesis of tris(4-imino-2-pentanonato)chromium,Cr[CH3C(NH)CHC(O)CH3]3

Tris(4-imino-2-pentanonato)chromium was prepared by solid-state synthesis under conditions of mechanical activation of a mixture of chromium(III) chloride and sodium 4-imino-2-pentanonate and characterized by IR spectroscopy, X-ray diffraction, and electronic absorption spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2227–2229, December, 1994.The present work was carried out as a part of Project No. 1.164 Mechanochemical Synthesis of Complex Compounds of The State Scientific and Technical Program Ecologically Safe Processes in Chemistry and Chemical Technology with the financial support of the Ministry of Science of the RF.