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171.
172.
DFT computational study of the mechanism of allyl halides carbonylation catalyzed by nickel tetracarbonyl 总被引:1,自引:0,他引:1
Bottoni A Miscione GP Novoa JJ Prat-Resina X 《Journal of the American Chemical Society》2003,125(34):10412-10419
A theoretical investigation at the DFT(B3LYP) level on the carbonylation reaction of allyl bromide catalyzed by nickel tetra-carbonyl Ni(CO)(4) is discussed. The computational results show the following: (i) Three main steps characterize the catalytic cycle: (a) an oxidative addition step, (b) a carbonylation step, and (c) a reductive elimination step where the acyl product is obtained and the catalyst is regenerated. (ii) Both Ni(CO)(3) and Ni(CO)(4) complexes can behave as "active" catalytic species. (iii) The oxidative addition leads to the formation of either eta(3) or eta(1)-allyl nickel complexes, which are involved in a fast equilibrium. (iv) The carbonylation occurs much more easily on the eta(1) than on the eta(3) intermediates. 相似文献
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174.
本文报道用Nicolet 170 SXFT-IR红外光谱仪观测磁疗手术胆结石、磁疗破碎排出胆结石及服中草药破碎胆结石的红外光谱,分析并比较了它们的光谱特征。 相似文献
175.
Paital AR Mitra T Ray D Wong WT Ribas-Ariño J Novoa JJ Ribas J Aromí G 《Chemical communications (Cambridge, England)》2005,(41):5172-5174
Based on a combined theoretical-experimental study, we propose that substituted m-phenylene ligands (m-N-Phi-N) can act as tuneable strong ferromagnetic couplers connecting Cu(II) ions; a new complex presenting that bridge with J close to +15 cm(-1) has been suggested and synthesized. 相似文献
176.
177.
178.
Reinoso S Vitoria P Gutiérrez-Zorrilla JM Lezama L San Felices L Beitia JI 《Inorganic chemistry》2005,44(26):9731-9742
Reaction of in situ generated copper(II)-monosubstituted Keggin polyoxometalates and copper(II)-bipyridine-oxalate complexes in the corresponding alkaline acetate buffer led to the formation of hybrid metal organic-inorganic compounds K(2)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(H(2)O)(2)(mu-ox)}(2)].14H(2)O (1), K(14)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}](2)[SiW(11)O(39)Cu(H(2)O)].55H(2)O (2), (NH(4))(4)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}].10H(2)O (3), and Rb(4)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}].10H(2)O (4). Their structures have been established by single-crystal X-ray diffraction. The main structural feature of these compounds is the presence of copper(II)-monosubstituted alpha-Keggin polyoxoanions as inorganic building blocks, on which the mu-oxalatodicopper metalorganic blocks are supported. Compound 1contains the discrete hybrid polyanion [{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(H(2)O)(2)(mu-ox)}(2)](2)(-), whereas the polymeric hybrid polyanion [{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}(2)](n)(4)(n)(-) gives a monodimensional character to compounds 2-4. Magnetic and EPR results are discussed with respect to the crystal structure of the compounds. DFT calculations on both the [Cu(2)(bpy)(2)(H(2)O)(4)(mu-ox)](2+) cationic complex and the metalorganic blocks have been performed in order to determine the optimized geometry and the magnetic coupling constants, respectively. 相似文献
179.
将酞菁锰(MnPc)掺入阳离子表面活性剂双十二烷基二甲基溴化铵(DDAB)的氯仿溶液,并涂布于热解石墨电极表面,待氯仿挥发后即制得MnPc-DDAB薄膜电极。循环伏安实验表明,在KBr溶液中,该薄膜电极有两对还原氧化峰,第一对峰的Epc1=-0.27V,Epa1=0.01V;第二对峰的Epc2=-0.76V,Epa2=-0.62V(vs.SCE)。本文着重探讨了第二对峰的电化学行为,估计了该体系的电荷传递扩散系数Dct和表观非均相电极反应速率常数K0′等电化学参数,并可将该薄膜电极用于催化三氯乙酸的电化学还原。 相似文献
180.
Let G be a non-compact connected semisimple Lie group with finite center and let GK denote the centralizer of a maximal compact subgroup K of G inG, the universal enveloping algebra over of the Lie algebra of G. In [4] Lepowsky defines an injective anti-homo morphism P:G
KK
MA, where M is the centralizer in K of a Cartan subalgebraa of the symmetric pair (G,K),K andA are the universal enveloping algebras over corresponding to K anda, respectively, andK
M is the centralizer of M inK. The subalgebra P(G
K) ofK
MA has considerable significance in the infinite dimensional representation theory of G. In this paper we explicitly compute P(G
K) when G=S0o(4,1), and show how this result leads to the determination of all irreducible representations of G and its universal covering group Spin(4,1).Partially supported by CONICET (Argentina) grants. 相似文献