: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Biochemistry of metallothionein

Light-Emitting Self-Assembled Materials Based on d(8) and d(10) Transition Metal Complexes.

Overview of metallothionein.

A stereochemical study of polyhedral eight-vertex structures is presented, based on continuous shape measures (CShM). Reference polyhedra, shape maps, and minimal-distortion interconversion paths are presented for eight-vertex polyhedral and polygonal structures within the CShM framework. The application of these stereochemical tools is analyzed for several families of experimental structures: 1) coordination polyhedra of molecular transition-metal coordination compounds, classified by electron configuration and ligands; 2) edge-bonded polyhedra, including cubane structures, realgar, and metal clusters; 3) octanuclear transition-metal supramolecular architectures; and 4) coordination polyhedra in extended structures in inorganic solids. Structural classification is shown to be greatly facilitated by these tools, and the detection of less common structures, such as the gyrobifastigium, is straightforward.

The Rich Stereochemistry of Eight‐Vertex Polyhedra: A Continuous Shape Measures Study

(Me 4 N) 2 [(μ-SPh) 6 (CdBr) 4 ] et (Me 4 N) 2 [(μ-SePh) 6 (CdBr 4 )] cristallisent dans le systeme cubique, groupe d'espace P2 1 3 et leur structure est affinee jusqu'a R=0,033

Syntheses of (Me4N)2[(.mu.-EPh)6(MX)4] (M = Cd, Zn; E = S, Se; X = Cl, Br, I). Crystal and molecular structures of (Me4N)2[(.mu.-EPh)6(CdBr)4] (E = S, Se) and characterization of [(.mu.-EPh)6(CdX)4]2- in solution by cadmium-113 and selenium-77 NMR

A multinuclear (1H, 13C, 113Cd) nuclear magnetic resonance and magnetic circular dichroism spectroscopic study of thiolate complexes of cadmium

Modelling cortical cataractogenesis. 13. Early effects on lens ATP/ADP and glutathione in the streptozotocin rat model of the diabetic cataract.

The salts (Ph(4)E)[M(SOCPh)(3)] (M = Zn, Cd, or Hg; E = P or As) are produced by the reaction of Zn(NO(3))(2).6 H(2)O, Cd(NO(3))(2).4H(2)O or HgCl(2) with Et(3)NH(+)PhCOS(-) and (Ph(4)E)X (E = P, X = Br; E = As, X = Cl) in aqueous MeOH in the ratios M(II):PhCOS(-):Ph(4)E(+) = 1:>/=3:>/=1. The crystal structures of (Ph(4)P)[Zn(SOCPh)(3)] (1), (Ph(4)As)[Cd(SOCPh)(3)] (2) and (Ph(4)P)[Hg(SOCPh)(3)] (3) have been determined by single-crystal X-ray diffraction experiments. Crystal data for 1: triclinic; space group Po; Z = 2; a = 10.819(2) A, b = 13.219(3) A, c = 15.951(3) A; alpha = 101.75(2) degrees, beta = 97.92(1) degrees, gamma = 109.18(2) degrees. Crystal data for 2: triclinic; space group Po; Z= 2; a = 10.741(2) A, b = 13.168(2) A, c = 15.809(2) A; alpha = 101.00(1) degrees, beta = 97.65(1) degrees, gamma = 109.88(1) degrees. Crystal data for 3: monoclinic; space group P2(1)/n; Z = 4; a = 13.302(2) A, b = 14.276(2) A, c = 21.108(2) A; beta = 90.92(1) degrees. The compounds 1 and 2 are isomorphous and isostructural. In the anions [M(SOCPh)(3)](-) the metal atoms have trigonal planar coordination by three sulfur atoms. The metal atoms are further more weakly coordinated intramolecularly to one (M = Hg) or two (M = Zn, Cd) thiobenzoate oxygen atom(s). Using the Bond Valence approach it is found that the contribution of M.O bonding to the total bonding is in the order Cd > Zn > Hg. The metal ((113)Cd, (199)Hg) NMR signals of [M(SOCPh)(3)](-) (M = Cd, Hg) are more shielded than those found for MS(3) kernels in thiolate complexes, a difference attributed to the M(.)O bonding in the thiobenzoate complexes. The (113)Cd resonance of [Cd(SOCPh)(3)](-) in dilute solution is in the region anticipated from dilution data for [Na(Cd{SOCPh}(3))(2)](-).

Chemistry of Thiobenzoates: Syntheses, Structures, and NMR Spectra of Salts of [M(SOCPh)(3)](-) (M = Zn, Cd, Hg).

Reaction of Cd(NO 3 ) 2 .4H 2 O, NaSOCPh, and Me 4 NCl in aqueous MeOH in ratios from 1:2.7:0.67 to 1:4:2 produces the salt (Me 4 N)(Na[Cd{SOCPh} 3 ] 2 ). The structure of 1 has been determined by single-crystal X-ray diffractometry techniques. Crystal data: triclinic, space group P1; Z=1; a=11.026(1), b=11.886(2), c=10.906(1) A; α= 94.32(1), β=113.25(1), γ=71.53(1) o ; V=1243.5(5) A 3 .

Synthesis, structure, and nuclear magnetic resonance spectra cadmium-111, sodium-23 of tetramethylammonium hexakis(thiobenzoato)(dicadmium sodium)ate. A trinuclear anion with cadmium in nearly trigonal planar coordination and sodium in octahedral coordination

Philip A. W. Dean

Papers

Syntheses of (Me4N)2[(.mu.-EPh)6(MX)4] (M = Cd, Zn; E = S, Se; X = Cl, Br, I). Crystal and molecular structures of (Me4N)2[(.mu.-EPh)6(CdBr)4] (E = S, Se) and characterization of [(.mu.-EPh)6(CdX)4]2- in solution by cadmium-113 and selenium-77 NMR

A multinuclear (1H, 13C, 113Cd) nuclear magnetic resonance and magnetic circular dichroism spectroscopic study of thiolate complexes of cadmium

Modelling cortical cataractogenesis. 13. Early effects on lens ATP/ADP and glutathione in the streptozotocin rat model of the diabetic cataract.

Chemistry of Thiobenzoates: Syntheses, Structures, and NMR Spectra of Salts of [M(SOCPh)(3)](-) (M = Zn, Cd, Hg).

Synthesis, structure, and nuclear magnetic resonance spectra cadmium-111, sodium-23 of tetramethylammonium hexakis(thiobenzoato)(dicadmium sodium)ate. A trinuclear anion with cadmium in nearly trigonal planar coordination and sodium in octahedral coordination