J. Appl. Cryst.の発刊に際して

1. Advantages of Chemical Redox Agents 878 2. Disadvantages of Chemical Redox Agents 879 C. Potentials in Nonaqueous Solvents 879 D. Reversible vs Irreversible ET Reagents 879 E. Categorization of Reagent Strength 881 II. Oxidants 881 A. Inorganic 881 1. Metal and Metal Complex Oxidants 881 2. Main Group Oxidants 887 B. Organic 891 1. Radical Cations 891 2. Carbocations 893 3. Cyanocarbons and Related Electron-Rich Compounds 894

/pdf/chemical-redox-agents-for-organometallic-chemistry-4fs84ntwp8.pdf

Chemical Redox Agents for Organometallic Chemistry

: 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

The development of microgels/nanogels for drug delivery applications

Advances in copper complexes as anticancer agents.

Treatment of [Rh2(µ-CO)(bipy)(dppe)(µ-N1,N3-RNNNR)2]2+12+[bipy = 2,2′-bipyridyl, dppe = 1,2-bis(diphenylphosphino)ethane, R =p-tolyl] with a catalytic amount of [NBun4][BH4] gave [Rh2(µ-CO)-(bipy)(dppe)(µ-N1,3,N3-RNNNR)(µ-N1,N3-RNNNR)]2+32+ X-ray studies on which show one ‘normal’ bridging triazenide ligand and one in which one of the terminal N atoms binds one Rh atom while the second bonds to both metal atoms; the triazenide ligands of 32+ are cis-bound to one metal centre and trans-bound to the second.

Redox-catalysed isomerisation of [Rh2(µ-CO)(bipy)(Ph2PCH2CH2PPh2)(µ-N1,N3-RNNNR)2]2+ to [Rh2(µ-CO)(bipy)(Ph2PCH2CH2PPh2)(µ-N1,3,N3-RNNNR)(µ-N1,N3-RNNNR)]2+(bipy = 2,2′-bipyridyl, R =p-tolyl); an unprecedented bonding mode for the bridging triazenide ligand

The crystal structures of three azonaphtharylamide pigments

Detailed comparison of the molecular structures of [1,2-μ-(C4H4)-3,3,3-(CO)3-3,1,2-closo-RuC2B9H9] (1) and [1,2-μ-(C4H6)-3,3,3-(CO)3-3,1,2-closo-RuC2B9H9] (2) reveals evidence for an Enhanced Structural Carborane Effect in 1 arising from the involvement of the cage pπ orbitals in the exopolyhedral ring to some degree. A minor co-product in the synthesis of 2 is [η-{1,2-μ-(C4H6)}-3,3-(CO)2-3,1,2-closo-RuC2B9H9] (3). Compounds 2 and 3 are readily interconverted, since heating 2 to reflux in THF or reaction with Me3NO affords 3 which readily reacts with CO to regenerate 2. The η-ene bonding in 3 is also displaced by PMe3, P(OMe)3 and t-BuNC to yield [1,2-μ-(C4H6)-3,3-(CO)2-3-PMe3-3,1,2-closo-RuC2B9H9] (4), [1,2-μ-(C4H6)-3,3-(CO)2-3-P(OMe)3-3,1,2-closo-RuC2B9H9] (5) and [1,2-μ-(C4H6)-3,3-(CO)2-3-t-BuNC-3,1,2-closo-RuC2B9H9] (6), respectively. Structural studies of 4–6, focussing on the Exopolyhedral Ligand Orientation of the {Ru(CO)2L} fragment relative to the C2B3 carborane face, are discussed in terms of the structural trans effects of PMe3, P(OMe)3 and t-BuNC relative to that of CO. An improved synthesis of [1,2-μ-(C6H4)2-1,2-closo-C2B10H10], “biphenylcarborane”, is reported following which the first transition-metal derivatives of this species, [1,2-μ-(C6H4)2-3-Cp-3,1,2-closo-CoC2B9H9] (7) and [1,2-μ-(C6H4)2-3,3,3-(CO)3-3,1,2-closo-RuC2B9H9] (8), are prepared. Comparisons of the structures of 7 and 8 with the corresponding benzocarborane derivatives [1,2-μ-(C4H4)-3-Cp-3,1,2-closo-CoC2B9H9] and 1, respectively, suggest that Clar's rule for aromaticity can be applied to polycyclic aromatic hydrocarbons fused onto carborane cages.

Further studies of the Enhanced Structural Carborane Effect: tricarbonylruthenium and related derivatives of benzocarborane, dihydrobenzocarborane and biphenylcarborane

Paramagnetic Tetrahedral Dinitrosyliron Complexes Containing Redoc-active Cyanomanganese Ligands

The title compound, C3H12B10O2 or 1-COOH-1,2-closo-C2B10H11, forms centrosymmetric dimers through intermolecular hydrogen bonding between the carboxylic acid groups, resulting in the formation of an eight-membered ring [R{_2^2}(8)]. The C=O bond of the carboxylic acid group almost eclipses the unsubstituted cage C atom, with a C—C—C—O torsion angle of 2.6 (2)°.

Georgina M. Rosair

Papers

Redox-catalysed isomerisation of [Rh2(µ-CO)(bipy)(Ph2PCH2CH2PPh2)(µ-N1,N3-RNNNR)2]2+ to [Rh2(µ-CO)(bipy)(Ph2PCH2CH2PPh2)(µ-N1,3,N3-RNNNR)(µ-N1,N3-RNNNR)]2+(bipy = 2,2′-bipyridyl, R =p-tolyl); an unprecedented bonding mode for the bridging triazenide ligand

The crystal structures of three azonaphtharylamide pigments

Further studies of the Enhanced Structural Carborane Effect: tricarbonylruthenium and related derivatives of benzocarborane, dihydrobenzocarborane and biphenylcarborane

Paramagnetic Tetrahedral Dinitrosyliron Complexes Containing Redoc-active Cyanomanganese Ligands

Crystal engineering with heteroboranes. I. 1-Carboxy-1,2-dicarba-closo-dodecaborane(11).