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排序方式: 共有188条查询结果,搜索用时 15 毫秒
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Eric J.L. McInnes Grigore A. Timco Richard E.P. Winpenny 《Coordination chemistry reviews》2005,249(23):2577-2590
Studies of two distinct classes of chromium(III) cage complexes are discussed. The first are compact oxo- and carboxylate cages, made by heating precursors to high temperature under a flow of nitrogen. One of these cages, [Cr12O9(OH)3(O2CCMe3)15], has an S = 6 spin ground state which proves a very interesting subject for study by EPR and MCD spectroscopy. Use of other carboxylates leads to other octa- and dodeca-nuclear complexes. The second class of compounds are homo- and hetero-metallic wheels and chains bridged by fluoride and carboxylates. These include the first heterometallic anti-ferromagnetically coupled ring systems and are being widely studied in areas as diverse as magnetic cooling and quantum information processing. The mechanism by which these unusual cyclic and acyclic structures form is discussed. 相似文献
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Collison D Goodgame DM Hitchman MA Lippert B Mabbs FE McInnes EJ 《Inorganic chemistry》2002,41(11):2826-2833
Multifrequency continuous wave EPR spectra (4-34 GHz) on a powder of the title compound are consistent with a spin-triplet state. This arises from interaction between centrosymmetrically related pairs of copper(II) ions in the solid. The spectra at all frequencies have been simulated with a single set of spin-Hamiltonian parameters. The results show that there is noncoincidence between the principal axes of the g-matrices on each copper center and those of the zero-field splitting (D) tensor. This noncoincidence is a single rotation of 33 degrees +/- 2 degrees. The parameters from the powder spectra have been verified by a subsequent single-crystal EPR study which yielded the spin-Hamiltonian parameters g(XX) = 2.074, g(YY) = 2.093, g(ZZ) = 2.385, D(XX) = +/-0.0228 cm(-1), D(YY) = +/-0.0211 cm(-1), D(ZZ) = -/+0.0439 cm(-1) with Euler angles of alpha = 179 degrees, chi = 33.4 degrees, and gamma = 328 degrees. Analysis of the zero-field splitting tensor in terms of exchange indicates that the interaction between the pairs of copper(II) ions is almost entirely dipolar in origin. This study shows that multifrequency EPR spectroscopy on powders, coupled with spectrum simulation, can detect and measure noncoincidence between the principal axes of the g-matrix and zero-field splitting tensor, and does not necessarily require the presence of metal hyperfine interactions. 相似文献
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Bould J McInnes YM Carr MJ Kennedy JD 《Chemical communications (Cambridge, England)》2004,(21):2380-2381
[(PMe2Ph)4Pt2B10H10] reversibly takes up atmospheric dioxygen to give the fluxional dioxygen-dimetallaborane complex [(PMe2Ph)4(O2)Pt2B10H10], which has Pt-Pt 2.7143(3), Pt-O 2.141(4) and 2.151(4) and O-O 1.434(6)A. 相似文献
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Branscombe ND Atkins AJ Marin-Becerra A McInnes EJ Mabbs FE McMaster J Schröder M 《Chemical communications (Cambridge, England)》2003,(9):1098-1099
Multi-frequency EPR spectroscopy on 61Ni-labelled samples of [Ni2(L)]3+ confirms extensive charge-delocalisation between the Ni(III) centre and thiolate donors in the Ni(II)Ni(III) complex. 相似文献
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Wang Q Barclay JE Blake AJ Davies ES Evans DJ Marr AC McInnes EJ McMaster J Wilson C Schröder M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(14):3384-3396
A novel [NiS4Fe2(CO)6]cluster (1: 'S(4)'=(CH(3)C(6)H(3)S(2))(2)(CH(2))(3)) has been synthesised, structurally characterised and has been shown to undergo a chemically reversible reduction process at -1.31 V versus Fc(+)/Fc to generate the EPR-active monoanion 1(-). Multifrequency Q-, X- and S-band EPR spectra of (61)Ni-enriched 1(-) show a well-resolved quartet hyperfine splitting in the low-field region due to the interaction with a single (61)Ni (I=3/2) nucleus. Simulations of the EPR spectra require the introduction of a single angle of non-coincidence between g(1) and A(1), and g(3) and A(3) to reproduce all of the features in the S- and X-band spectra. This behaviour provides a rare example of the detection and measurement of non-coincidence effects from frozen-solution EPR spectra without the need for single-crystal measurements, and in which the S-band experiment is sensitive to the non-coincidence. An analysis of the EPR spectra of 1(-) reveals a 24 % Ni contribution to the SOMO in 1(-), supporting a delocalisation of the spin-density across the NiFe(2) cluster. This observation is supported by IR spectroscopic results which show that the CO stretching frequencies, nu(CO), shift to lower frequency by about 70 cm(-1) when 1 is reduced to 1(-). Density functional calculations provide a framework for the interpretation of the spectroscopic properties of 1(-) and suggest that the SOMO is delocalised over the whole cluster, but with little S-centre participation. This electronic structure contrasts with that of the Ni-A, -B, -C and -L forms of [NiFe] hydrogenase in which there is considerable S participation in the SOMO. 相似文献
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Reducing the use of solvents is an important aim of green chemistry. Using micelles self-assembled from amphiphilic molecules dispersed in water (considered a green solvent) has facilitated reactions of organic compounds. When performing reactions in micelles, the hydrophobic effect can considerably accelerate apparent reaction rates, as well as enhance selectivity. Here, we review micellar reaction media and their potential role in sustainable chemical production. The focus of this review is applications of engineered amphiphilic systems for reactions (surface-active ionic liquids, designer surfactants, and block copolymers) as reaction media. Micelles are a versatile platform for performing a large array of organic chemistries using water as the bulk solvent. Building on this foundation, synthetic sequences combining several reaction steps in one pot have been developed. Telescoping multiple reactions can reduce solvent waste by limiting the volume of solvents, as well as eliminating purification processes. Thus, in particular, we review recent advances in “one-pot” multistep reactions achieved using micellar reaction media with potential applications in medicinal chemistry and agrochemistry. Photocatalyzed reactions in micellar reaction media are also discussed. In addition to the use of micelles, we emphasize the process (steps to isolate the product and reuse the catalyst). 相似文献
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Conrad A. P. Goodwin Dr. Floriana Tuna Prof. Eric J. L. McInnes Prof. Stephen T. Liddle Dr. Jonathan McMaster Dr. Inigo J. Vitorica‐Yrezabal Dr. David P. Mills 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(45):14579-14583
We report the synthesis and characterization of the uranium(III) triamide complex [UIII(N**)3] [ 1 , N**=N(SiMe2tBu)2?]. Surprisingly, complex 1 exhibits a trigonal planar geometry in the solid state, which is unprecedented for three‐coordinate actinide complexes that have exclusively adopted trigonal pyramidal geometries to date. The characterization data for [UIII(N**)3] were compared with the prototypical trigonal pyramidal uranium(III) triamide complex [UIII(N“)3] (N”=N(SiMe3)2?), and taken together with theoretical calculations it was concluded that pyramidalization results in net stabilization for [UIII(N“)3], but this can be overcome with very sterically demanding ligands, such as N**. The planarity of 1 leads to favorable magnetic dynamics, which may be considered in the future design of UIII single‐molecule magnets. 相似文献