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51.
Chemaly SM Jack LA Yellowlees LJ Harper PL Heeg B Pratt JM 《Dalton transactions (Cambridge, England : 2003)》2004,(14):2125-2134
Studies of the emission spectra of four Co(III) cobinamides (diaquo-, aquohydroxo-, dihydroxo- and dicyano-) show (1) that the excited states corresponding to the alphabeta and epsilon absorption bands behave like the S(1) and S(2) levels in the non-alternant hydrocarbon azulene (with emission from S(2)> S(1) in violation of Kasha's rule) and (2) that the excited states include a TICT (twisted intramolecular charge transfer) mechanism, as in the simpler cyanines, but where the TICT state gives rise to dual fluorescence instead of cis-trans isomerisation. Combined with the previously reported dual fluorescence from the S(1) level in synthetic metal corrinoids and in the naturally-occurring metal-free corrin, this provides evidence that the existence of an additional (metastable) ground state with a significantly different vibronic splitting and nuclear configuration is an intrinsic property of the basic corrin ligand (irrespective of the nature of the side-chains and the metal ion or even the absence of a metal) which distinguishes it from porphyrin. The occurrence of hysteresis (and its associated oscillations) in redox reactions of the cobinamides involving both the Co(III/II) and Co(II/I) couples indicates that the corrin ligand also has an intrinsic ability to exist in different conformations or "allosteric" forms with differing redox potential, which further distinguishes it from the porphyrin ligand. Possible links between the existence of an additional metastable ground state and of allosteric changes and the likely reasons for the selection of corrin over a porphyrin for the vitamin B(12)-dependent enzymes are discussed. 相似文献
52.
Eric G. Bryan Brian F.G. Johnson Jack Lewis 《Journal of organometallic chemistry》1976,122(2):249-252
Treatment of H2Os3(CO)10 with cyclonona-l,2-diene produced HOs3(CO)9C9H13 and Os2(CO)6(C9H4)2. Single crystal X ray analysis has shown that the latter is not isostructural with Fe2(CO)6(C9H14)2. 相似文献
53.
Jack H. Lunsford 《Angewandte Chemie (International ed. in English)》1995,34(9):970-980
One of the great challenges in the field of heterogeneous catalysis is the conversion of methane to more useful chemicals and fuels. A chemical of particular importance is ethene, which can be obtained by the oxidative coupling of methane. In this reaction CH4 is first oxidatively converted into C2H6, and then into C2H4. The fundamental aspects of the problem involve both a heterogeneous component, which includes the activation of CH4 on a metal oxide surface, and a homogeneous gas-phase component, which includes free-radical chemistry. Ethane is produced mainly by the coupling of the surface-generated CH radicals in the gas phase. The yield of C2H4 and C2H6 is limited by secondary reactions of CH radicals with the surface and by the further oxidation of C2H4, both on the catalyst surface and in the gas phase. Currently, the best catalysts provide 20% CH4 conversion with 80% combined C2H4 and C2H6 selectivity in a single pass through the reactor. Less is known about the nature of the active centers than about the reaction mechanism; however, reactive oxygen ions are apparently required for the activation of CH4 on certain catalysts. There is spectroscopic evidence for surface O? or O ions. In addition to the oxidative coupling of CH4, cross-coupling reactions, such as between methane and toluene to produce styrene, have been investigated. Many of the same catalysts are effective, and the cross-coupling reaction also appears to involve surface-generated radicals. Although a technological process has not been developed, extensive research has resulted in a reasonable understanding of the elementary reactions that occur during the oxidative coupling of methane. 相似文献
54.
A time-independent coupled-channel method, using hyperspherical coordinates, has been developed for calculating quantum mechanical collision-induced dissociation probabilities for collinear atom-diatom systems in which the exchange reaction can also occur. The results for a model potential energy surface are compared with quasi-classical trajectory calculations and discussed. 相似文献
55.
Sadowsky JD Schmitt MA Lee HS Umezawa N Wang S Tomita Y Gellman SH 《Journal of the American Chemical Society》2005,127(34):11966-11968
Molecules that bind to specific surface sites on proteins are of great interest from both fundamental and practical perspectives. We are exploring a ligand development strategy that is based on oligomers with discrete folding propensities ("foldamers"); we target a specific cleft on the cancer-associated protein Bcl-xL because this system is well characterized structurally. In vivo, this cleft binds to alpha-helical segments (BH3 domains) of other proteins. We evaluated several types of helical foldamer, built entirely from beta-amino acid residues or from mixtures of alpha- and beta-amino acid residues, and ultimately identified foldamers in the latter class that bind very tightly to Bcl-xL. Our results suggest that combining different types of foldamer backbones will be an effective and general strategy for creating high-affinity and specific ligands for protein surface sites. 相似文献
56.
We report the synthesis and physical studies of a novel porphyrazine (pz) dimer [1[Ni,Cu]]2, which has Ni(II) ions incorporated into the pz cores and is linked by two Cu(II) ions coordinated to bis(picolinamide) chelates attached to the pz periphery. [1[Ni,Cu]]2 was prepared from precursor pz 2 with a selenodiazole ring fused to the pz core. This ring was deprotected to form the diamino-pz 3, which reacted with 2 mol of picolinoyl chloride hydrochloride to form pz 1[2H,2H], with peripheral bis(picolinamide) chelates; this was metalated to form [1[Ni,Cu]]2. The crystal structures of 1[2H,2H] and [1[Ni,Cu]]2 are presented. The latter is a dimer in which parallel, face-to-face pz's with an average separation of 3.30 angstroms are linked through the peripheral picolinamide ligands by a pair of peripheral Cu(II) ions. Each Cu(II) is coordinated with distorted square-planar geometry by a picolinamide from each pz. In this report, we focus on the interaction of these two peripheral Cu(II) ions. We discuss the preparation and magnetic properties of the pz dimer complex [1[Ni,Cu]]2 with two Cu(II) ions in the peripheral chelate but a diamagnetic metal ion Ni(II) in the pz core. Although [1[Ni,Cu]]2 contains two Cu(II) ions (S = 1/2), we could detect no electron paramagnetic resonance signal, which suggests very strong antiferromagnetic exchange between those two Cu(II) ions. Temperature-dependent magnetic susceptibility measurement gives an exchange splitting between the S = 0 ground state and the excited triplet state of delta = 660 cm(-1). 相似文献
57.
Condensation of allylborane reagents 9 and 12 with aldehydes gave anti-3-[(diphenylmethylene)amino]-1-alken-4-ols 10 and 13 with high relative and absolute stereocontrol. Subsequent deprotection gave the corresponding free anti-3-amino-1-alken-4-ols 11 and 14. Alternatively, reaction of imines 13a, 13f, and 13g with trifluoromethanesulfonic anhydride and acidic methanol gave, via rearrangement, double inversion, and hydrolysis, the isomeric anti-4-amino-1-alken-3-ols 22, 38a, and 38b in good yield. The stereochemistry of the rearrangement products has been established by a single crystal X-ray study of compound 37 and by chemical correlation. 相似文献
58.
The coupled-cluster approach to obtaining the bond-state wave functions of many-electron systems is extended, with a set of physically reasonable approximations, to admit a multiconfiguration reference state. This extension permits electronic structure calculations to be performed on correlated closed- or open-shell systems with potentially uniform precision for all molecular geometries. Explicit coupled cluster working equations are derived using a multiconfiguration reference state for the case in which the so-called cluster operator is approximated by its one- and two-particle components. The evaluation of the requisite matrix elements is facilitated by use of the unitary group generators which have recently received wide attention and use in the quantum chemistry community. 相似文献
59.
The structures, energies, and natural atomic charges of 2-dimethylaminophenol oxide, 2-Me2N-(O)C6H4OH, and 2-dimethylphosphinylphenol, 2-Me2P(O)C6H4OH, in three different conformations were computed at the ab initio MP2/6-31G* level. Computed natural charges indicate distributions of electron density in amine oxides and phosphine oxides that are quite different from what is normally assumed on the basis of the formal charges in the usual representations of these compounds. The charges on nitrogen and phosphorus in these compounds are typically computed to be approximately zero on nitrogen and +2 on phosphorus, and the oxygen is considerably more negative in the phosphine oxide than in the amino oxide. Electronegativity differences thus play a larger role and formal charges a smaller one in determining atomic charges in these compounds than is generally believed. Despite the more negative oxygen in phosphine oxides, amine oxides are computed to be considerably more basic when participating in hydrogen bonding. Calculations treating the computed natural charges on these six conformations as point charges for classical approximations of the coulombic energies support the idea that the quantum mechanically computed relative energies are largely determined by coulombic interactions. 相似文献
60.
Summary.
A coupled semilinear elliptic problem modelling an
irreversible, isothermal chemical reaction is introduced, and
discretised using the usual piecewise linear Galerkin finite element
approximation. An interesting feature of the problem is that a reaction order of
less than one gives rise to a "dead core" region. Initially,
one
reactant is assumed to be acting as a catalyst and is kept constant. It
is shown that error bounds previously obtained for a scheme involving
numerical integration can be improved upon by considering a quadratic regularisation
of the nonlinear term.
This technique is then applied to the full coupled problem, and optimal
and error bounds
are proved in the absence of
quadrature. For a scheme involving numerical integration,
bounds similar to those
obtained for the catalyst problem are shown to hold.
Received May 25, 1993 / Revised version received July 5, 1994 相似文献