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1.
Olefin cross-metathesis (CM) is potentially an attractive method for generating dynamic combinatorial libraries (DCLs). In order for the CM reaction to be useful for DCL production, the course of the reaction and product distribution must be relatively insensitive to functionality remote from the reacting centers. We report on the CM of a series of allyl- and homoallylamides that are strongly dependent on remote functionality. This includes an unusual example of a cis-selective CM. [Reaction: see text] 相似文献
2.
The compounds (L-N3)MoO(qdt) and (L-N3)MoO(tdt) [(L-N3) = hydrotris(3,5-dimethyl-1-pyrazolyl)borate; tdt = toluene-3,4-dithiolate; qdt = quinoxaline-2,3-dithiolate] have been studied by cyclic voltammetry and photoelectron, magnetic circular dichroism, and electronic absorption spectroscopies, and the experimental data have been interpreted in the context of ab initio molecular orbital calculations on a variety of dithiolate dianion ligands. The PES data reveal very substantial differences between (L-N3)MoO(qdt) and (L-N3)MoO(tdt) in that the first ionization (originating from the Mo dxy orbital) for (L-N3)MoO(qdt) is about 0.8 eV to deeper binding energy than that of (L-N3)MoO(tdt). This stabilizing effect is also reflected in the solution reduction potentials, where (L-N3)MoO(qdt) is approximately 220 mV easier to reduce than (L-N3)MoO(tdt). A direct correlation between the relative donating ability of a given dithiolate ligand and the reduction potential of the (L-N3)MoO(dithiolate) complex has been observed, and a linear relationship exists between the calculated Mulliken charge on the S atoms of the dithiolate dianion and the Mo reduction potential. The study confirms previously communicated work (Helton, M. E.; Kirk, M. L. Inorg. Chem. 1999, 38, 4384-4385) that suggests that anisotropic covalency contributions involving only the out-of-plane S orbitals of the coordinated dithiolate control the Mo reduction potential by modulating the effective nuclear charge of the metal, and this has direct relevance to understanding the mechanism of ferricyanide inhibition in sulfite oxidase. Furthermore, these results indicate that partially oxidized pyranopterins may play a role in facilitating electron and/or atom transfer in certain pyranopterin tungsten enzymes which catalyze formal oxygen atom transfer reactions at considerably lower potentials. 相似文献
3.
The electronic structure of cis,trans-(L-N(2)S(2))MoO(X) (where L-N(2)S(2) = N,N'-dimethyl-N,N'-bis(2-mercaptophenyl)ethylenediamine and X = Cl, SCH(2)C(6)H(5), SC(6)H(4)-OCH(3), or SC(6)H(4)CF(3)) has been probed by electronic absorption, magnetic circular dichroism, and resonance Raman spectroscopies to determine the nature of oxomolybdenum-thiolate bonding in complexes possessing three equatorial sulfur ligands. One of the phenyl mercaptide sulfur donors of the tetradentate L-N(2)S(2) chelating ligand, denoted S(180), coordinates to molybdenum in the equatorial plane such that the OMo-S(180)-C(phenyl) dihedral angle is approximately 180 degrees, resulting in a highly covalent pi-bonding interaction between an S(180) p orbital and the molybdenum d(xy) orbital. This highly covalent bonding scheme is the origin of an intense low-energy S --> Mo d(xy) bonding-to-antibonding LMCT transition (E(max) approximately 16000 cm(-)(1), epsilon approximately 4000 M(-)(1) cm(-)(1)). Spectroscopically calibrated bonding calculations performed at the DFT level of theory reveal that S(180) contributes approximately 22% to the HOMO, which is predominantly a pi antibonding molecular orbital between Mo d(xy) and the S(180) p orbital oriented in the same plane. The second sulfur donor of the L-N(2)S(2) ligand is essentially nonbonding with Mo d(xy) due to an OMo-S-C(phenyl) dihedral angle of approximately 90 degrees. Because the formal Mo d(xy) orbital is the electroactive or redox orbital, these Mo d(xy)-S 3p interactions are important with respect to defining key covalency contributions to the reduction potential in monooxomolybdenum thiolates, including the one- and two-electron reduced forms of sulfite oxidase. Interestingly, the highly covalent Mo-S(180) pi bonding interaction observed in these complexes is analogous to the well-known Cu-S(Cys) pi bond in type 1 blue copper proteins, which display electronic absorption and resonance Raman spectra that are remarkably similar to these monooxomolybdenum thiolate complexes. Finally, the presence of a covalent Mo-S pi interaction oriented orthogonal to the MOO bond is discussed with respect to electron-transfer regeneration in sulfite oxidase and Mo=S(sulfido) bonding in xanthine oxidase. 相似文献
4.
5.
D. McNaughton 《Structural chemistry》1992,3(4):245-252
The infrared spectrum of dichloroacetylene, prepared by the pyrolysis of dichloromaleic anhydride at 1000°C, has been recorded at both low and high resolution. In the low resolution spectrum a number of combination bands not previously observed have been assigned, the infrared active fundamentals have been reassigned, and a center wavenumber value has been determined for the Raman activev
1 fundamental. The high resolution spectra of a number of fundamental bands, summation bands, and one difference band for the isotopomers,35CICC35CI and35CICC37CI, have been assigned, while a more limited number of bands has been assigned for the species37CICC37CI and35CI13CC35CI. The resultant rotational and vibration-rotation constants have been used to obtainr
o,r
e,r
s, and partial rs structural parameters. The most reliable bond lengths are obtained from the partialr
s treatment and are 164.105(53) pm for the C-CI bond and 119.203(79) pm for the CC bond. 相似文献
6.
J.A. Edgington V.J. Howard I.M. Blair B.E. Bonner F.P. Brady M.W. McNaughton 《Nuclear Physics A》1974,218(1):151-168
We have measured the double differential cross section for bremsstrahlung production in neutron-proton collisions near 130 MeV. Outgoing nucleons were detected at eight pairs of angles simultaneously. The cross sections agree with several theoretical predictions for those four angle pairs in which the proton emerged at 20° (θ = 20°), but are larger than expected in the four cases that θp = 32°. The method of data reduction, and the sources of uncertainty, are discussed in detail. 相似文献
7.
V.J. Howard J.A. Edgington S.S.Das Gupta I.M. Blair B.E. Bonner F.P. Brady M.W. McNaughton N.M. Stewart 《Nuclear Physics A》1974,218(1):140-150
We have measured the np (nd) elastic scattering cross sections at 25(17) angles in the interval 30°–168° (c.m.), using a neutron beam with a broad spectrum peaked near 130 MeV. At backward angles the outgoing charged particles from a liquid hydrogen (deuterium) target were detected; at forward angles we detected neutrons scattered from a hydrogenated (deuterated) scintillating target. Cross sections have been normalized to the energy dependent solution of the Livermore nucleon-nucleon partial wave analysis, evaluated at 130 MeV. The np measurements represent a marginal improvement on previous work; the nd cross sections show some differences from pd measurements, in agreement with earlier indications at an energy of 152 MeV. 相似文献
8.
Bane MK Robertson EG Thompson CD Appadoo DR McNaughton D 《The Journal of chemical physics》2011,135(22):224306
High-resolution FTIR spectra of the short lived species ketenimine have been recorded in the region 700-1300 cm(-1) and over 1500 transitions of the ν(10) and ν(6) modes have been assigned. Effective rotational and centrifugal distortion parameters for the v(10) = 1 and v(6) = 1 (excluding K(a) = 5) states were determined by co-fitting transitions, and treating strong a- and c-axis Coriolis interactions between them. Other perturbations attributed to interactions with the v(8) = 2 and v(12) = 1 + v(8) = 1 dark-states were also observed and treated. The ν(10) transitions are predicted to be inherently very weak, but are enhanced by an intensity stealing effect with the highly IR active ν(6) mode. A mechanism for this intensity stealing in ketenimine is also detailed. 相似文献
9.
Keiichi Ohno Hiroatsu Matsuura Don McNaughton Harold W. Kroto 《Journal of Molecular Spectroscopy》1985,111(2):415-424
The infrared spectra of 1-phosphapropyne, CH3CP, and its perdeuteride, CD3CP, have been measured in the gaseous and solid states. The QK branches of perpendicular bands have been analyzed in terms of the usual quadratic expression in K. Fermi resonances were identified for the ν1, ν2 + ν3, 2ν3, 2ν60; and ν5, 2ν3 + ν8 band systems of CH3CP and the ν1, 2ν3, 2ν60; ν6, ν7 + ν8; and ν7, 3ν81 band systems of CD3CP. The xy Coriolis interaction was also identified between the ν3 and ν6 bands of the two species. All the fundamentals were assigned and the normal coordinate treatment was carried out along with the Coriolis constants, ζz. 相似文献
10.
Dunbar AD Richardson TH McNaughton AJ Hutchinson J Hunter CA 《The journal of physical chemistry. B》2006,110(33):16646-16651
The visible absorption spectra of various substituted porphyrin compounds both in chloroform solution and as Langmuir-Blodgett (LB) solid-state films have been investigated. The porphyrin compounds examined were the Zn, Sn, Mg, and free base derivatives of 5,10,15,20-tetrakis[3,4-bis(2-ethylhexyloxy)phenyl]-21H,23H-porphine (EHO). Changes in the absorption spectra of these materials induced by their exposure to various organic compounds are reported with a view toward determining whether this is a useful approach toward an optical gas sensor. 相似文献