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211.
Solid-state ligand dynamics in interpenetrating Mn[N(CN)(2)](2)(pyrazine): a neutron spectroscopy study 总被引:1,自引:0,他引:1
We have used quasielastic neutron scattering to probe the solid-state ligand dynamics in the coordination polymer Mn[N(CN)(2)](2)(pyz) [pyz = pyrazine] which has double-interpenetrating 3D lattices. A reversible structural phase transition occurs at 410 K as shown by neutron spectroscopy and differential scanning calorimetry. The origin of this transition is linked to rotational dynamics associated with the bridging pyz ligands. At 425 K, the pyrazine ring motion can be solely regarded as a 180 degrees reorientational jump about the axis defined by the Mn-N coordinative bonds, occurring with a correlation time of approximately 70 ps. This model can be extended to the 200-410 K temperature region using high-resolution backscattering spectroscopy to measure an identical motion on the time scale of nanoseconds with an activation energy of 24 +/- 2 kJ mol(-1). In contrast, no quasielastic scattering is seen for the 2D layered variant beta-Cu[N(CN)(2)](2)(pyz), owing to its more compact layer packing motif. Importantly, this work represents the very first study of solid-state rotational dynamics in an interpenetrating lattice structure. 相似文献
212.
Unrestricted density functional theory (UB3LYP), CASSCF, and CASPT2 calculations have been employed to compute the relative energies of the C(s) and C(2v) geometries of several 1,5-disubstituted semibullvalenes. Substitution at these positions with R = F, -CH(2)-, or -O- affords semibullvalenes that are predicted to have C(2v) equilibrium geometries. Calculated singlet-triplet energy splittings and the energies of isodesmic reactions are used to assess the amount of bishomoaromatic character at these geometries. The results of these calculations show that employing strain to destabilize the C(s) geometries of semibullvalenes can lead to a significant decrease in the amount of bishomoaromatic stabilization of the C(2v) geometries, due to reduced through-space interaction between the two allyl groups. However, the C(2v) equilibrium geometries of the 1,5-disubstituted semibullvalenes with R = F and -RR- = -O- do benefit from stabilizing through-bond interactions between the two allyl groups. These interactions involve mixing of the bisallyl HOMO with the low-lying C-F or C-O sigma orbital combinations of the same symmetry. In contrast, for -RR- = -CH(2)-, through-bond interactions destabilize the bisallyl HOMO and are predicted to make the ground state of this semibullvalene a triplet. 相似文献
213.
Swanson MI She YM Ens W Brown EG Coombs KM 《Rapid communications in mass spectrometry : RCM》2002,16(24):2317-2324
Mammalian reovirus is an enteric virus that contains a double-stranded RNA genome. The genome consists of ten RNA segments that encode eight structural and three non-structural proteins. The structural proteins form a double-layered structure. The innermost layer, called the core, consists of five proteins (lambda1, lambda2, lambda3, micro 2, and sigma2). Protein lambda3 is the RNA-dependent RNA polymerase (RdRp) and micro 2 is thought to be an RdRp cofactor. Translation of most reovirus proteins is known to commence at the first start codon. However, the translation initiation site of the viral core protein micro 2, encoded by the M1 RNA segment, has been in dispute. Although the theoretical molecular weight of micro 2 is 83 267 Da the actual molecular weight is unknown because micro 2 runs aberrantly in SDS-PAGE and has resisted characterization by Edman degradation, indicating that the amino terminus is post-translationally modified. In this study, we used proteolysis coupled with MALDI-Qq-TOFMS to determine that translation of micro 2 initiates at the first AUG codon, that its actual molecular weight approximates the theoretical value of 83 kDa, that the amino terminal methionine residue is removed, and that the next amino acid (alanine) is post-translationally acetylated. 相似文献
214.
Cigang Xu Emmanuel Flahaut Sam R. Bailey Gareth Brown Jeremy Sloan Karl S. Coleman V. Clifford Williams Malcolm L. H. Green * . Inorganic Chemistry Laboratory University of Oxford Oxford OX QR UK 《高等学校化学研究》2002,18(2):130-132
IntroductionSingle walledcarbonnanotubes(SWNTs)havebeensynthesisedbyusingvariousmethods[1— 3] andthechemicalvapourdeposition (CVD )methodhasbeenconsideredasa promisingmethodto produceSWNTsonanindustrialscale[3— 5] .However ,alltheSWNT productssynthesisedtodateco… 相似文献
215.
Craig M. Anderson Garrett Brown Matthew W. Greenberg David Yu Nellie Bowen Rahma Ahmed Melissa Yost-Bido Alina Wray 《Tetrahedron letters》2019,60(43):151156
Several thiophene-based N^C ligands were synthesized. Strategically, a bromide was incorporated on the 2-position of the thiophene ring. When allowed to react with the platinum tetramethyl dimer, [Pt2Me4(µ-SMe2)2], platinum(IV) platinacycles were formed by oxidative addition of the C(sp2)-X bond. These platinum(IV) compounds were characterized by NMR and HRMS. The platinum (IV) compounds were subsequently subjected to thermolysis. A series of reactions occurred, including selective C-C reduction elimination and selective C-H oxidative addition, giving mixtures of platinum(II) products with varying degrees of regioselectivity. 相似文献
216.
Yuki Matsumoto Takafumi Yamamoto Kousuke Nakano Hiroshi Takatsu Taito Murakami Kenta Hongo Ryo Maezono Hiraku Ogino Dongjoon Song Craig M. Brown Cdric Tassel Hiroshi Kageyama 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(3):766-769
Square‐planar coordinate Ni2+ ions in oxides are exclusively limited to a low‐spin state (S=0) owing to extensive crystal field splitting. Layered oxychalcogenides A2NiIIO2Ag2Se2 (A=Sr, Ba) with the S=1 NiO2 square lattice are now reported. The structural analysis revealed that the Ni2+ ion is under‐bonded by a significant tensile strain from neighboring Ag2Se2 layers, leading to the reduction in crystal field splitting. Ba2NiO2Ag2Se2 exhibits a G‐type spin order at 130 K, indicating fairly strong in‐plane interactions. The high‐pressure synthesis employed here possibly assists the expansion of NiO2 square lattice by taking the advantage of the difference in compressibility in oxide and selenide layers. 相似文献
217.
Liang‐An Chen Alan R. Lear Pin Gao M. Kevin Brown 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(32):11072-11076
A method for the construction of boron‐substituted quaternary carbons or diarylquaternary carbons by arylboration of highly substituted alkenylarenes is presented. A wide range of alkenes and arylbromides can participate in this reaction thus allowing for a diverse assortment of products to be prepared. In addition, a solvent dependent regiodivergent arylboration of 1,2‐disubstituted alkenylarenes is presented, thus greatly increasing the scope of products that can be accessed. 相似文献
218.
219.
Gonzales JM Barden CJ Brown ST Schleyer Pv Schaefer HF Li QS 《Journal of the American Chemical Society》2003,125(4):1064-1071
The adiabatic electron affinities of cyclopentadiene and 10 associated benzannelated derivatives have been predicted with both density functional and Hartree-Fock theory. These systems can also be regarded as benzenoid polycyclic aromatic hydrocarbons (PAHs) augmented with five-membered rings. Like the PAHs, the electron affinities of the present systems generally increase with the number of rings. To unequivocally bind an electron, cyclopentadiene must have at least two conventionally fused benzene rings. 1H-Benz[f]indene, a naphthalene-annulated cyclopentadiene, is predicted to have a zero-point energy corrected adiabatic electron affinity of 0.13 eV. Since the experimental E(A) of naphthalene is negative (-0.19 eV), the five-membered ring appendage contributes to the stability of the naphthalene-derived 1H-benz[f]indene radical anion significantly. The key to binding the electron is a contiguous sequence of fused benzenes, since fluorene, the isomer of 1H-benz[f]indene, with separated six-membered rings, has an electron affinity of -0.07 eV. Each additional benzene ring in the sequence fused to cyclopentadiene increases the electron affinity by 0.15-0.65 eV: the most reliable predictions are cyclopentadiene (-0.63 eV), indene (-0.49 eV), fluorene (-0.07 eV), 1H-benz[f]indene (0.13 eV), 1,2-benzofluorene (0.25 eV), 2,3-benzofluorene (0.26 eV), 12H-dibenzo[b,h]fluorene (0.65 eV), 13H-indeno[1,2-b]anthracene (0.82 eV), and 1H-cyclopenta[b]naphthacene (1.10 eV). In contrast, if the six-membered ring-fusion is across the C(2)-C(3) cyclopentadiene single bond, only a single benzene is needed to bind an electron. The theoretical electron affinity of the resulting molecule, isoindene, is 0.49 eV, and this increases to 1.22 eV for 2H-benz[f]indene. The degree of aromaticity is responsible for this behavior. While the radical anions are stabilized by conjugation, which increases with the size of the system, the regular indenes, like PAHs in general, suffer from the loss of aromatic stabilization in forming their radical anions. While indene is 21 kcal mol(-1) more stable than isoindene, the corresponding radical anion isomers have almost the same energy. Nucleus-independent chemical shift calculations show that the highly aromatic molecules lose almost all aromaticity when an extra electron is present. The radical anions of cyclopentadiene and all of its annulated derivatives have remarkably low C-H bond dissociation energies (only 18-34 kcal mol(-1) for the mono-, bi-, and tricyclics considered). Hydrogen atom loss leads to the restoration of aromaticity in the highly stabilized cyclopentadienyl anion congeners. 相似文献
220.