Synthesis and Reactivity of the First Isolated Hydrogen‐Bridged Silanol–Silanolate Anions

We report on the first examples of isolated silanol–silanolate anions, obtained by utilizing weakly coordinating phosphazenium counterions. The silanolate anions were synthesized from the recently published phosphazenium hydroxide hydrate salt with siloxanes. The silanol–silanolate anions are postulated intermediates in the hydroxide‐mediated polymerization of aryl and alkyl siloxanes. The silanolate anions are strong nucleophiles because of the weakly coordinating character of the phosphazenium cation, which is perceptible in their activity in polysiloxane depolymerization.     

1H-CRAMPS Solid-State NMR and X-Ray Crystal Studies of Inclusion Complexes Formed from 3,3′-bis(9-Hydroxy-9-fluorenyl)-2,2′-binaphthyl Hosts with Acetone

The crystal structures of inclusion compounds of 3,3-bis(9-hydroxy-9-fluorenyl)-2,2-binaphthyl host (1) and its chloro (2) or bromo (3) derivatives substituted in 2,7-positions of the fluorene units with acetone guests (1A–3A) were determined by X-ray studies as well as by ¹H-CRAMPS solid-state NMR. Using this NMR technique allows identification of differently bound guest molecules due to their different chemical shifts caused by the influence of the ring current effects of the host aryl units.     

Efficient search for all low energy conformations of polypeptides by Monte Carlo methods

The Metropolis Monte Carlo method has been added to the program FANTOM for energy refinement of polypeptides and proteins using a Newton–Raphson minimizer in torsion angle space. With this extension, different strategies for global minimization of the semiempirical energy function ECEPP/2 by various temperature schedules and restriction of conformational space were tested for locating local minimum conformations with low energy of the pentapeptide Met-enkephalin. In total, 1881 conformations below ?10 kcal/mol were found. These conformations could be represented by 77 nonidentical conformations which were analysed for their pattern of hydrogen bonds, types of tight turn, pairwise root-mean-square-deviation (rmsd), Zimmermann codes and side chain conformations. All low energy conformations below ?10.4 kcal/mol show strong similarity to the global minimum conformation in the backbone structure.     

Structures and magnetic properties of tetranuclear nickel(II) complexes with unusual mu3-1,1,3 azido bridges

Pyrazolate-based dinucleating ligands with thioether-containing chelate arms have been used for the synthesis of a family of novel tetranuclear nickel(II) complexes [L2Ni4(N3)3(O2CR)](ClO4)2 that incorporate three azido bridges and one carboxylate (R = Me, Ph). Molecular structures have been elucidated by X-ray crystallography in four cases, revealing Ni4 cores with a unique topology in which two of the azido ligands adopt an unusual mu3-1,1,3 bridging mode. The compounds were further characterized by mass spectrometry, IR spectroscopy, and variable-temperature magnetic susceptibility measurements. Magnetic data analyses indicate a combination of significant intramolecular ferromagnetic and antiferromagnetic exchange interactions that give rise to an overall S(T) = 0 ground state. The sign and the magnitude of the individual couplings have been rationalized in the framework of the common magnetostructural correlations for end-to-end and end-on azido linkages, suggesting that these correlations also remain valid for the respective fragments of multiply bridging mu3-1,1,3 azido ligands.     

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.     

Electrochemical and kinetic study of oxygen in a perfluorotributylamine emulsion

Oxygen can be determined in a perfluorotributylamine emulsion used as a blood substitute by coulometry and polarography. The oxygen uptake of the emulsion (4.3 × 10^?3 mol l^?1 or 11 ml-% at 25°C and P_O2 = 760 mm Hg) is about three times greater than that of water. The adsorption of surfactant on a dropping mercury electrode changes the electrochemical parameters E_{$\text{1}\text{2}$}, α and k₃. The marked difference between the diffusion coefficients of oxygen and hydrogen peroxide (ratio 2.6) seems to be proceed from the ejection of oxygen molecules from the perfluorotributylamine droplets and from the insolubility of hydrogen peroxide molecules in the droplets. The constant rate of oxygen release by these droplets was estimated to be 10⁴ s^?1 by a stopped-flow spectrophotometric method. This constant rate seems to be linked with the particle diameter (0.2 μm) and the diffusion coefficient in the perfluorotributylamine droplets (1.6 × 10^?6 cm² s^?1).     

Minimization of empirical energy functions in proteins including hydrophobic surface area effects

We present analytical expressions to calculate the gradient of the water-accessible surface area of proteins with respect to Cartesian coordinates and dihedral angles. A detailed mathematical analysis leads to corrected equations for the gradient calculation used previously in the ANAREA program. To study the hydrophobic effect of solvent-protein interactions, our expressions have been implemented to further improve the program package FANTOM. We used this version of FANTOM to minimize the ECEPP/2 and the hydrophobic energy of tendamistat. © 1993 John Wiley & Sons, Inc.     

Reaction of 5,6,7,8-Tetrahydropterin with Iron(III) Acetylacetonate. Detection of Radical Cations by Electrospray Ionization Mass Spectrometry

The experimental conditions developed for the detection of rather stable radical cations in solution by electrospray-ionization mass spectrometry (ESI-MS) of a Fe^II complex of 2-amino-5,6,7,8-tetrahydro-5-methylpteridin-4 (3H)-one ( 1c ) are used to observe the formation of the more unstable radical cations formed from 2-amino-5,6,7,8-tetrahydropteridin-4(3H)-one ( 1a ) and tris(pentane-2,4-dionato)iron(III) ([Fe^III(acac)₃]; 4 ) and to monitor their oxidation to the corresponding p-quinonoid dihydropterin complexes. These results contribute to the understanding of the important role played by 6β-5,6,7,8-tetrahydro-L -biopterin ( 1b ; a homologue of 1a ) together with iron as constituent of some cofactors. The complexes obtained from 1a and iron may be considered, e.g. as a model of the cofactor of the phenylalanine hydroxylase. Moreover, we describe an improved synthesis of 1c .     

Synthesis and Characterization of Sterically Encumbered Derivatives of Aluminum Hydrides and Halides: Assessment of Steric Properties of Bulky Terphenyl Ligands

The synthesis and characterization of several sterically encumbered monoterphenyl derivatives of aluminum halides and aluminum hydrides are described. These compounds are [2,6-Mes(2)C(6)H(3)AlH(3)LiOEt(2)](n)() (1), (Mes = 2,4,6-Me(3)C(6)H(2)-), 2,6-Mes(2)C(6)H(3)AlH(2)OEt(2) (2), [2,6-Mes(2)C(6)H(3)AlH(2)](2) (3), 2,6-Mes(2)C(6)H(3)AlCl(2)OEt(2) (4), [2,6-Mes(2)C(6)H(3)AlCl(3)LiOEt(2)](n)() (5), [2,6-Mes(2)C(6)H(3)AlCl(2)](2) (6), TriphAlBr(2)OEt(2) (7), (Triph = 2,4,6-Ph(3)C(6)H(2)-), [2,6-Trip(2)C(6)H(3)AlH(3)LiOEt(2)](2) (8) (Trip = 2,4,6-i-Pr(3)C(6)H(2)-), 2,6-Trip(2)C(6)H(3)AlH(2)OEt(2) (9), [2,6-Trip(2)C(6)H(3)AlH(2)](2) (10), 2,6-Trip(2)C(6)H(3)AlCl(2)OEt(2) (11), and the partially hydrolyzed derivative [2,6-Trip(2)C(6)H(3)Al(Cl)(0.68)(H)(0.32)(&mgr;-OH)](2).2C(6)H(6) (12). The structures of 2, 3a, 4, 6, 7, 9a, 10a, 10b, 11, and 12 were determined by X-ray crystallography. The structures of 3a, 9a, 10a, and 10b, are related to 3, 9, and 10, respectively, by partial occupation of chloride or hydride by hydroxide. The compounds were also characterized by (1)H, (13)C, (7)Li, and (27)Al NMR and IR spectroscopy. The major conclusions from the experimental data are that a single ortho terphenyl substituent of the kind reported here are not as effective as the ligand Mes (Mes = 2,4,6-t-Bu(3)C(6)H(2)-) in preventing further coordination and/or aggregation involving the aluminum centers. In effect, one terphenyl ligand is not as successful as a Mes substituent in masking the metal through agostic and/or steric effects.