Models for the Active Center of Pterin-Containing Molybdenum Enzymes: Crystal structure of a molybdenum complex with sulfur and pterin ligands

The first crystal structure of a molybdenum complex 9 with a hydrogenated pterin and a sulfur ligand contributes to the discussion about the active center of molybdenum and tungsten enzymes containing a molybdopterin cofactor. Complex 9 was synthesized through a redox reaction of [Mo^VIO₂ (LN-S₂)] ( 8 ; LN-S₂ = pyridine-2, 6-bis(methanethiolato)) with 5, 6, 7, 8-tetrahydropterin ( 7 ). 2 HCl (H₄Ptr.2 HCl). The complex crystallizes, with a non-coordinating Cl-atom acting as a counterion, in the monoclinic space group C2/c (No. 15) with cell dimensions a = 22.900(5), b = 10.716(2), c = 17.551(4) Å, β = 120.36(3)°, and Z = 8. We interpret 9 as [Mo^IVO(LN-S₂)(H⁺-q-H₂Ptr)]Cl (q = quinonoid; H₂Ptr = dihydropterin), i.e., a Mo^IV monooxo center coordinated by a pyridine-2, 6-bis(methanethiolato) ligand and a protonated dihydropterin. The spectroscopic properties of this new complex are comparable to those of other crystalline molybdenum complexes of hydrogenated pterins without additional S-coordination. The slightly H₂O-soluble complex 9 reacts with the natural enzyme substrate DMSO very slowly, possibly due to the lack of easily dissociable ligands at the metal center.     

Energy-dispersive x-ray laue measurements with anomalous dispersion effects

By using an energy dispersive solid state detector, harmonics were separated in a Lauetype diffraction experiment with a single crystal and white primary radiation (Bremsstrahlung) from a conventional x-ray tube. Intensity changes around the absorption edge of an atom species in the crystal could be verified according to theory.Dedicated to Prof. Dr. H.E. Müser on the occasion of his 60th birthday     

Dynamics of vector spin glasses with random anisotropy

The dynamics of vector spin glasses with additional random anisotropy is investigated in the mean field approximation. We find a cross-over of the upper critical line from a behaviour of Heisenberg spins with a field-temperature dependence , for large fieldsH, to Ising like behaviourT _f –TT ^2/3 , for small fields and fixed anisotropy, in agreement with results of Kotliar and Sompolinsky. Here, andT _f are characteristic spin glass temperatures. In addition, one has a second line with reversed behaviour which presumably represents a cross-over line from weak to strong non-ergodicity. The local transverse susceptibility _T () varies for large fields and 0 along the upper critical line as ^vT , with a critical exponentV _T = 1/2 – 11D/60 J, whereD andJ are the anisotropy and exchange coupling constants, respectively. On the Ising-like part of the upper critical line one has isotropic spin glass parameters,q _L =q _T , and susceptibilities, and a critical exponent, which is similar to that of Ising spins along the de Almeida-Thouless line.Dedicated to B. Mühlschlegel on the occasion of his 60th birthdaySFB Aachen-Jülich-Köln     

σ,π-acetylido complexes via P---C bond cleavage of phosphinoacetylenes: X-ray structure of Fe2(CO)6(CCPh)(PPh2)

Solutions of Co^II salts of organic acids in primary amines absorb molecular oxygen rapidly and irreversibly forming μ-dioxygen—cobalt complexes. Thermolysis leads to a homopolar cleavage of the OO bond with subsequent radical reactions involving ligand amine. After thermolysis the capacity of oxygen uptake is reestablished (catalysis).     

Synthesis,Structure, and Optical Properties of Terminally Sulfur‐Functionalized Core‐Substituted Naphthalene‐Bisimide Dyes

The synthesis, characterization, and optical properties of a series of new 2,6‐disubstituted naphthalene‐bisimide dyes as molecular rods comprising terminal AcS groups is reported. The first series of dyes ( 1 – 3 ), comprising phenylhetero (Ph‐X) core substituents, cover a broad range of the VIS spectrum, ranging from yellow ( 2 ) over red ( 3 ) to blue ( 1 ). The second series of dyes contains benzylhetero (Bn‐X) core substituents ( 4 – 7 ). For the same heteroatom connecting the substituent to the naphthalene core, both series were found to display comparable colors. For the second series, the colors were blue ( 4 ), red ( 5 ), and violet ( 6, 7 ). The Ph‐X‐substituted dyes 1 – 3 are nonfluorescent, in contrast to the Bn‐X‐substituted compounds 4 – 7 . This rich variety of optical features that can be adjusted by rather small alterations of the core substituents makes these structurally very comparable molecular rods ideal candidates for optically triggered molecular‐transport investigations. Also, thanks to the terminal AcS groups, these compounds can be placed between nobel‐metal electrodes for optically triggered transport experiments.     

The Radical Anions of N,N′-Dicyanoquinone Diimines,a New Class of Electron Acceptors

The radical anions of 12 N,N′-dicyanoquinone diimines, a new class of electron acceptors, hace been characterized by their hyperfine data with the use of ESR and ENDOR spectroscopy. The largest coupling constant (0.30–0.45 mT), due to the two ¹⁴N nuclei in the exocyclic positions, gives rise to a conspicuous broadening of the peripheral ESR lines by an incomplete averaging of the hyperfine anisotropy. The most plausible interpretation of the experimental results for the radical anions of N,N′-dicyano- 1,4-benzoquinone diimine ( 1 ) and N,N′-Dicyano-9,10-anthraquinone diimine ( 9 ) is in terms of both ‘syn’- and ‘anti’-configurations contributing to the ESR and ENDOR spectra and having equal proton- and ¹⁴N-coupling constants. The π-spin distribution in the radical anions of N,N′-dicyanoquinone diimines is compared with those in the analogous ions of tetracyanoquinodimethanes and quinones.     

LCAO-MO-berechnungen an schwefelhaltigen π-elektronensystemen—XXXIV : Nichtbindende S,S-wechselwirkung in polymethinfarbstoffen

Sulfur-containing polymethine dyes exhibit anomalous chromophoric properties. The vinylene shift of the first two homologues is often considerably larger or smaller than the shift between higher members of the series. Moreover, the absorption wavelengths of non-symmetrical dyes with sulfur-containing groups, as calculated by the mean value rule differ from the experimental data, but not in the predicted manner.This deviation is caused by an interannular no-bond SS-interaction in the monomethine ion. This conclusion is supported by the spectra of appropriately-substituted dyes and is substantiated by theoretical considerations. Starting from the well-known symmetry properties of polymethine MO's the simple PMO-method reproduces correctly the effects of the p_π-type overlap between atomic orbitals of adjacent S atoms at long wavelength absorptions: The SS-interactions lead to a hypsochromic shift in monomethines with (4N + 2)π-electrons (N = 1,2…) and to a bathochromic shift in monomethines with (4N)π-electrons.