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21.
Cronin L McGregor PA Parsons S Teat S Gould RO White VA Long NJ Robertson N 《Inorganic chemistry》2004,43(25):8023-8029
The "one-pot" synthesis and characterization of a large 28-mer macrocycle (H(4)L(2)) with oxamido units capable of complexing guest ions through oxygen or nitrogen donor atoms is reported. Single-crystal structure determination of H(8)L(2)(NO(3))(4) and (Cu(2)[H(2)L(2)](H(2)O)(2))(NO(3))(2) demonstrated that the macrocycle contains two sites capable of complexing two nitrate anions or two copper(II) ions, involving a large structural reorganization in the conformation of the macrocyclic framework on coordination of the copper(II) ions when compared to the nitrate. Electrochemical and magnetic susceptibility measurements on the dinuclear Cu(II) complex and the related mononuclear and trinuclear Cu(II) complexes derived from the related 14-mer macrocycle were carried out and illustrate the role of the oxamido groups in mediating metal-metal interaction and delocalization. 相似文献
22.
The bis(chelated) complex of CrV(0) derived from the dianion (L2
−) of 2-ethyl-2-hydroxybutanoic acid is readily reduced to a bis(chelate of CrIII, featuring the monoanion (LH−) [Cr
V(0)(L2−)2]−+4H++H2O+2e−→[CrIII(OH2)2(LH−
2]+ of this acid. Potentials estimated by Ghosh in 1993 for this 2e− change, E0 (pH 0) 1.32 V, Eeff (pH 3.3) 0.93 V, are in accord with the nearly irreversible reductions of the Cr(V) species (in 1∶1 ligand buffer) by Fe2+, V02+, IrCl6
3
− and I−, whereas lower values reported by Bose in 1996, E0 (pH 0) 0.84 V, Eeff (pH 3.3) 0.45 V, are potentiometrically inconsistent with these conversions. A similar discrepancy is noted for potentials
for Cr(V,IV) estimated in 1996, E0 (pH 0) 0.84 V, Eeff (pH 3.3) 0.46 V, which, wholly contrary to observation, predict that the reductions of excess Cr(V) to CR(IV) by Fe2+, V02+, and I− are thermodynamically disfavored. 相似文献
23.
The labeling pattern obtained from incorporation of a mixture of sodium [1-13C]- and [s-13C]acetates has confirmed the irregular derivation of the benz[α]anthraquinone skeleton of the angucycline antibiotic PD 116198. Subsequent incorporation of sodium [1-13C, 18O2]-, and [1-13C, 2-2H3]acetates and of 18O2 have revealed the origins of the hydrogen and oxygen atoms of the antibiotic. The possibility of a “two-chain” biosynthesis was tested by feeding 2H-labeled orsellinates; however, no incorporation was detected. PD 116198 seems most plausibly derived by rearrangement of an initially-formed linear tetracyclic intermediate. 相似文献
24.
This is the final paper in a series of three directed toward the evaluation of spin-dependent Hamiltonians. In this paper we derive the reduced matrix elements of the U(2n) generators in a basis symmetry adapted to the subgroup U(n) × U(2) (i.e., spin-orbit basis), for the representations appropriate to many-electron systems. This enables a direct evaluation of the matrix elements of spin-dependent Hamiltonians in the spin-orbit basis. An alternative (indirect) method, which employs the use of U(2n) ↓ U(n) × U(2) subduction coefficients, is also discussed. 相似文献
25.
This paper is the first in a series of two directed toward a unitary calculus for group-function-type approaches to the many-electron correlation problem. In this paper we present a complete derivation of the matrix elements of the U(n = n1 + n2) generators, for the representations approapriate to many-electron systems, in a basis symmetry adapted to the subgroup U(n1) × U(n2). Explicit formulae for the fundamental U(n):U(n1) × U(n2) reduced Wigner coefficients, which are needed for the general multishell problem, are also obtained. The symmetry properties of the reduced Wigner coefficients and reduced matrix elements are investigated, and a suitable phase convention is given. 相似文献
26.
Lynch CL Hale JJ Budhu RJ Gentry AL Finke PE Caldwell CG Mills SG MacCoss M Shen DM Chapman KT Malkowitz L Springer MS Gould SL DeMartino JA Siciliano SJ Cascieri MA Carella A Carver G Holmes K Schleif WA Danzeisen R Hazuda D Kessler J Lineberger J Miller M Emini E 《Organic letters》2003,5(14):2473-2475
[reaction: see text] A novel approach to alpha,alpha-disubstituted-beta-amino acids (beta(2,2)-amino acids) was employed in the synthesis of a series of 3-(pyrrolidin-1-yl)propionic acids possessing high affinity for the CCR5 receptor and potent anti-HIV activity. The rat pharmacokinetics for these new analogues featured higher bioavailabilities and lower rates of clearance as compared to cyclopentane 1. 相似文献
27.
Jakob Boelsterli Ursula Eggnauer Esteban Pombo-Villar Hans-Peter Weber Malcolm Walkinshaw Robert O. Gould 《Helvetica chimica acta》1992,75(2):507-512
The l-azabicyclo[2.2.1]heptan-3-exo-ol ( 2 ) was resolved by fractional crystallisation of its hydrogen tartrate salts. The enantiomers (+)- and (?)- 2 were oxidised to the ketones (?)- 4 and (+)- 4 , respectively (Scheme). CD spectroscopy suggested that (?)- 4 possesses the (1R,4S)-configuration. This absolute configuration was confirmed by single-crystal X-ray diffraction of the derivative (+)-(1R,4R)-3-(1,3-dithian-2-ylidene)-1-azabicyclo [2.2.1]-heptane ((+)- 5 ). 相似文献
28.
29.
M. D. Gould 《Letters in Mathematical Physics》1992,24(3):183-196
It is shown that the braid generator is diagonalizable on arbitrary tensor product modules V V, V an irreducible module for a quantum group. A generalization of the Reshetikhin form for the braid generator is thereby obtained in the general case. As an application, a general closed formula is determined for link polynomials. 相似文献
30.