Dimolybdenum bis((S,S,S)-triisopropanolaminate(3-)): a blue compound with an unusual Mo-Mo triple bond

Mo2(OtBu)6 and Mo2(NMe2)6 each react with (S,S,S)-triisopropanolamine (2 equiv) in benzene to yield dimolybdenum bis((S,S,S)-isopropanolaminate(3-)), Mo2[(OC-(S)-HMeCH2)3N]2 (M identical to M), as a blue crystalline solid. Cell parameters at -160 degrees C: a = 17.389(6) A, b = 10.843(3) A, c = 10.463(3) A, beta = 125.28(1) degrees, Z = 2 in space group C2. The molecular structure involves an Mo2 unit inside an O6N2 distorted cubic box. The Mo2 axis is disordered about three positions with occupancy factors of ca. 45%, 45%, and 10%. Despite this disorder, the molecular structure is shown to contain a central Mo identical to Mo unit of distance 2.15(3) A coordinated to two triolate ligands which each have two chelating arms and one that spans the Mo identical to Mo bond. The local Mo2O6N2 moiety has approximate C2h symmetry, and the Mo-N distances are long, 2.4 A. The 1H and 13C(1H) NMR spectra recorded in benzene-d6 are consistent with the geometry found in the solid-state structure. The blue color arises from weak absorptions, epsilon approximately 150 dm3 mol-1 cm-1, at 580 and 450 nm in the visible region of the electronic absorption spectrum. Raman spectra recorded in KCl reveal pronounced resonance effects with excitation wavelengths of 488.0, 514.5, and 568.2 nm, particularly for the 322 cm-1 band, which can probably be assigned to nu(Mo identical to Mo). The electronic structure of this compound is investigated by B3LYP DFT calculations, and a comparison is made with the more typical ethane-like (D3d) Mo2(OR)6 compounds is presented. The distortion imposed on the molecule by the triisopropanolaminate(3-) ligands removes the degeneracy of the M-M pi molecular orbitals. The HOMO and SHOMO are both M-M pi and M-O sigma* in character, while the LUMO is M-M pi* and the SLUMO is predominantly M-O sigma* with metal sp character. The calculated singlet-singlet transition energies are compared with those implicit in the observed electronic spectrum.     

Aqueous cholesteric liquid crystals using uncharged rodlike polypeptides

The aqueous, lyotropic liquid-crystalline phase behavior of the alpha-helical polypeptide, poly(N(epsilon)-2-[2-(2-methoxyethoxy)ethoxy]acetyl-lysine) (1), has been studied using optical microscopy and X-ray scattering. Solutions of optically pure 1 were found to form cholesteric liquid crystals at volume fractions that decreased with increasing average chain length. At very high volume fractions, the formation of a hexagonal mesophase was observed. The pitch of the cholesteric phase could be varied by a mixture of enantiomeric samples L-1 and D-1, where the pitch increased as the mixture approached equimolar. The cholesteric phases could be untwisted, using either magnetic field or shear flow, into nematic phases, which relaxed into cholesterics upon removal of field or shear. We have found that the phase diagram of 1 in aqueous solution parallels that of poly(gamma-benzyl glutamate) in organic solvents, thus providing a useful system for liquid-crystal applications requiring water as solvent.     

Theoretical investigations of Fe porphyrins. V. Low-lying electronic states of bisammineporphinatoiron(III)

Ab initio CI calculations are reported on the lowest doublet, quartet, and sextet states of [Fe^III(P)(NH₃)₂]⁺. The low-spin ground state is calculated as (d_xy² (d_π)³ with d_xy(d_π)⁴ higher by 0.15 eV. The near-ir bands at ～1 eV observed in low-spin ferriheme proteins are attributed to (π → d_π) transitions. The lowest high-spin state is ⁶A_1g, and the near-ir transitions of the high-spin ferriheme proteins observed at ～1.2 eV are attributed to higher ⁶[tripsextet] excited states [i.e., ring triplet, metal sextet]. The 30-ps “triplet” transient populated with low quantum yield observed in laser-flash studies on Fe^III(TPP)CI [TPP = tetrapbenylporphyrin] may be an ¹[tripsextet] state.     

Matrix elements for spin-adapted configurations

It is shown that the turn-over rule which is used to simplify matrix elements between spin-projected Slater determinants may also be used to simplify formation of matrix elements between any orthonormal set of spin-coupled Slater determinants. The coefficients for the spin-coupling may then be chosen freely to reduce the number of important configurations in the secular equation.     

Extraction of ergosterol from peaty soils and determination by high performance liquid chromatography

The ergosterol content of soil can be used as an indicator of fungal activity. A method has been developed for the extraction and determination of ergosterol in organic soils, as part of a study to assess the correlation between fungal activity and the sequestration of metal pollutants. The moisture content of the soil affected the extraction process. Four consecutive extractions with methanol removed >95% of the ergosterol that can be obtained from the fresh sample (63% moisture) by exhaustive extraction. By freeze drying the soils prior to extraction (a) up to 35% more ergosterol was extracted after a single extraction, (b) >90% of the recoverable ergosterol was collected in two extractions and (c) the repeatability of the extraction was improved. Storage of soil extracts in the absence of light prevents degradation of ergosterol. A previously reported method for determination of ergosterol by HPLC has been improved by modification of the eluant composition. With 46% methanol/46% acetonitrile/8% dichloromethane, ergosterol was eluted with good resolution approximately 8 min after injection of 20 mul of the extract. The detection limit of the HPLC method was 0.5 mug/ml ergosterol, equivalent to 0.06 mug/g in 25 g fresh soil. Changes in ergosterol contents of peaty soil treated with fungicide, and in samples of the peaty podzol and a humus iron podzol in the vicinity of fungal fruiting bodies, have been determined.     

N2 activation by iron-sulfur complexes

Inspired by the determination of the structure of the nitrogenase enzyme cofactor by Rees et al., the binding of an N₂ molecule to some model iron-sulfur compounds was investigated usingab initio calculations. Side-on and end-on coordination to one two and four iron centers were investigated. In most cases, the N₂ is loosely bound and retains its internal triple bond, but a few examples are found where the N₂ is “activated” and has a longer N-N bond length.     

Chemical Vapor Deposition of Silicon Dioxide by Direct-Current Corona Discharges in Dry Air Containing Octamethylcyclotetrasiloxane Vapor: Measurement of the Deposition Rate

Experiments in a positive-polarity, wire/plate electrode establish the effects of the concentration of octamethylcyclotetrasiloxane (150–1100 ppm) and the operating current (0.5–2.55 μA/cm length of wire) on the rate of deposition of silicon dioxide on the high voltage wire. The wire is 100 μm radius tungsten and the wire-to-plate spacing is 1.5 cm. Analyses of the deposit with X-ray diffraction, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy show that it is amorphous silicon dioxide. The deposition rate increases linearly with increasing silicone concentration and corona current. For the concentrations of silicone likely to present in indoor air, the gas-phase processes limit the rate of deposition.