Computational study of the aminolysis of 2-benzoxazolinone

Three possible mechanisms (zwitterionic, neutral stepwise, and neutral concerted) of the ring-opening reaction of 2-benzoxazolinone (BO) upon aminolysis with methylamine were studied at the B3LYP/6-31G* level. In the gas phase, the neutral concerted mechanism is shown to be most favorable, which proceeds via a rate-determining barrier of 28-29 kcal/mol. The transition state, CTS, associated with this barrier is a four-centered one, where 1,2-addition of the N[bond]H of methylamine to the C[bond]O of BO ring occurs. The rate-determining barrier of the neutral stepwise pathway is found to be ca. 42 kcal/mol. The inclusion of solvent effects by a polarizable continuum model (PCM) does not change the conclusions based on the gas-phase study; the barrier at CTS is reduced to 20, 20, and 22 kcal/mol in water, ethanol, and acetonitrile, respectively.     

Theoretical study of isomerization by a 1,2-hydrogen shift in HAB molecules and HAB+ ions with 10 valence electrons

The potential-energy surfaces (PES's) of HAB molecules and HAB⁺ ions with the diatomic cores AB=CN^–, BO^–, BeF^–, N₂, CO, BF, CP^–, BS^–, NP, CS, BCl, SiN^–, AlO^–, SiO, AlF, SiP^–, AlS^–, P₂, SiS, and AlCl, which contain 10 valence electrons, have been calculated by the nonempirical MO-LCAO-SCF method with subsequent consideration of electron correlation in the framework of the third-order Møller—Plesset (MP3) method, and the isomerization realized by a 1,2-hydrogen shift in them has been studied. The similarities and differences in the form of the PES's corresponding to the migration of Li⁺ (which was previously investigated) and the migration of H⁺ around AB have been traced, and the geometric characteristics and relative energies of the isomers, as well as the heights of the activation barriers between them, have been compared. An attempt has been made to relate the differences in the properties to differences in the electronic structure of HAB and LiAB.Institute of New Chemical Problems, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 32, No. 2, pp. 3–11, March–April, 1991.     

Metal-peroxo versus metal-oxo oxidants in non-heme iron-catalyzed olefin oxidations: computational and experimental studies on the effect of water

Computational and experimental studies show that Fe(BPMEN)-catalyzed olefin oxidation has two (FeIII-OOH and FeV=O) oxidant species, which act with comparable activation barriers. The presence of water favors formation of an HO-FeV=O oxidant via water-assisted O-OH bond cleavage and leads to both epoxide and cis-diol products. In the absence of water, the oxidant is the FeIII-OOH [or (MeCN)FeIII-OOH], and oxidation mainly leads to epoxide. This conclusion differs from that derived from DFT investigations of iron-porphyrin-catalyzed olefin epoxidation, where the FeIII-OOH pathway is deemed too high in energy to be plausible. The difference between these two systems may lie in the more flexible coordination environment of the non-heme iron complex, which has an available adjacent coordination site that contributes to the activation of the peroxide in both wa and nwa pathways.     

An experimental and density functional study of the Sb–C bond activation and organo-Rh bond formation from the spontaneous decay of [RhCl3(SbPh3)3]

The reaction of RhCl₃ with SbPh₃ that produces mer-[RhCl₃(SbPh₃)₃] 1 and trans,mer-[RhCl₂(Ph)(SbPh₃)₃] 2 [A. Cavaglioni, R. Cini, J. Chem. Soc., Dalton Trans. (1997) 1149 (and references cited therein)], as well as the transformation of 1 to 2, was studied in details using the UV–Vis spectroscopy and density functional approaches. We elucidated the mechanism of Sb–C(Ph) bond activation and Rh–C(Ph) bond formation during these processes. Experimental studies show that the first step of the reaction of RhCl₃ with SbPh₃ is the formation of 1, which later rearranges to complex 2 via a concerted mechanism. The transition state associated with this transformation includes the Rh(III) center (hepta-coordinate) that interacts with three Cl^? ligands, two Sb-centers of SbPh₃ ligands, and one Sb–Ph bond of the third SbPh₃ ligand. The Cl^? ligand, trans to Sb, bridges Rh and Sb atom from the third SbPh₃ ligand. A possible pathway involving rhodium(I) intermediate species was also taken into account. The calculated geometry parameters of models of complexes 1 and 2 are in good agreement with the available X-ray data. Presented relative energies of the studied reactions are in good agreement with the relative yields of 1 and 2.     

A dodecanuclear Zn cluster sandwiched by polyoxometalate ligands

A dodecazinc silicotungstate K(20)Na(2)[Zn(6)(OH)(7)(H(2)O)(Si(2)W(18)O(66))](2)·34H(2)O (1) has been synthesized and characterized by X-ray crystallography, elemental analysis, infrared, UV-vis spectroscopy, cyclic voltammetry, acid-base titration, and DFT calculations. The twelve zinc atoms between the two [Si(2)W(18)O(66)](16-) frameworks make this complex more stable hydrolytically than the heteropolytungstate ligands, [Si(2)W(18)O(66)](16-), themselves. The structurally unique central Zn(12) core is formed by the fusion of two [Zn(6)(OH)(7)(H(2)O)](5+) units through two edge-sharing Zn6 atoms. DFT B3LYP calculations give HOMO-LUMO and (HOMO - 1)-LUMO energy gaps of ～3.65 and 3.91 eV, respectively, as compared to the band gap in ZnO of 3.35 eV.     

Does dinitrogen hydrogenation follow different mechanisms for [(eta5-C5Me4H)2Zr]2(mu2,eta2,eta2-N2) and {[PhP(CH2SiMe2NSiMe2CH2)PPh]Zr}2(mu2,eta2,eta2-N2) complexes? A computational study

The mechanisms of dinitrogen hydrogenation by two different complexes--[(eta(5)-C(5)Me(4)H)(2)Zr](2)(mu(2),eta(2),eta(2)-N(2)), synthesized by Chirik and co-workers [Nature 2004, 427, 527], and {[P(2)N(2)]Zr}(2)(mu(2),eta(2),eta(2)-N(2)), where P(2)N(2) = PhP(CH(2)SiMe(2)NSiMe(2)CH(2))(2)PPh, synthesized by Fryzuk and co-workers [Science 1997, 275, 1445]--are compared with density functional theory calculations. The former complex is experimentally known to be capable of adding more than one H(2) molecule to the side-on coordinated N(2) molecule, while the latter does not add more than one H(2). We have shown that the observed difference in the reactivity of these dizirconium complexes is caused by the fact that the former ligand environment is more rigid than the latter. As a result, the addition of the first H(2) molecule leads to two different products: a non-H-bridged intermediate for the Chirik-type complex and a H-bridged intermediate for the Fryzuk-type complex. The non-H-bridged intermediate requires a smaller energy barrier for the second H(2) addition than the H-bridged intermediate. We have also examined the effect of different numbers of methyl substituents in [(eta(5)-C(5)Me(n)H(5)(-)(n))(2)Zr](2)(mu(2),eta(2),eta(2)-N(2)) for n = 0, 4, and 5 (n = 5 is hypothetical) and [(eta(5)-C(5)H(2)-1,2,4-Me(3))(eta(5)-C(5)Me(5))(2)Zr](2)(mu(2),eta(2),eta(2)-N(2)) and have shown that all complexes of this type would follow a similar H(2) addition mechanism. We have also performed an extensive analysis on the factors (side-on coordination of N(2) to two Zr centers, availability of the frontier orbitals with appropriate symmetry, and inflexibility of the catalyst ligand environment) that are required for successful hydrogenation of the coordinated dinitrogen.     

Nonlinear intensity-related magneto-optical Kerr effects in the planar geometry

The reflection of an electromagnetic wave at the second-harmonic frequency from a semi-infinite optically isotropic magnetic medium for the directions of uniform magnetization corresponding to the meridional and equatorial Kerr effects is considered. Using the Green’s tensor function technique, in the first approximation in magnetization, the expressions for complex amplitudes of the field are obtained for the s and p polarizations of the incident beam and their superpositions. It is shown that in the latter case, the meridional effect becomes intensity-related. Dependences of the intensity-related meridional and equatorial Kerr effects on the angle characterizing polarization of the pump wave are obtained by numerical calculations. A comparative analysis of the linear and nonlinear Kerr effects is made.     

Dyadic Mappings and Dyadic Superparacompact Topological Groups

We introduce the notion of a dyadic superparacompactum which generalizes the classical notion of a dyadic bicompactum and give an analog of V. I. Kuz’minov and L. N. Ivanovskii’s Theorem on dyadicity of the space of a bicompact topological group for superparacompact groups. Moreover, we generalize L. S. Pontryagin’s Theorem on existence of an open bicompact subgroup in each neighborhood of unity of a locally bicompact totally disconnected topological group.Original Russian Text Copyright © 2005 Musaev D. K.__________Translated from Sibirskii Matematicheskii Zhurnal, Vol. 46, No. 4, pp. 851–859, July–August, 2005.     

Extending Metal‐to‐Polyoxometalate Charge Transfer Lifetimes: The Effect of Heterometal Location

In an effort to develop robust molecular sensitizers for solar fuel production, the electronic structure and photodynamics of transition‐metal‐substituted polyoxometalates (POMs), a novel class of compound in this context, was examined. Experimental and computational techniques including femtosecond (fs) transient absorption spectroscopy have been used to study the cobalt‐containing Keggin POMs, [Co^IIW₁₂O₄₀]^6? ( 1 a ), [Co^IIIW₁₂O₄₀]^5? ( 2 a ), [SiCo^II(H₂O)W₁₁O₃₉]^6? ( 3 a ), and [SiCo^III(H₂O)W₁₁O₃₉]^5? ( 4 a ), finding the longest lived charge transfer excited state so far observed in a POM and elucidating the electronic structures and excited‐state dynamics of these compounds at an unprecedented level. All species exhibit a bi‐exponential decay in which early dynamic processes with time constants in the fs domain yield longer lived excited states which decay with time constants in the ps to ns domain. The initially formed states of 1 a and 3 a are considered to result from metal‐to‐polyoxometalate charge transfer (MPCT) from Co^II to W, while the longer‐lived excited state of 1 a is tentatively assigned to a localized intermediate MPCT state. The excited state formed by the tetrahedral cobalt(II) centered heteropolyanion ( 1 a ) is far longer‐lived (τ=420 ps in H₂O; τ=1700 ps in MeCN) than that of 3 a (τ=1.3 ps), in which the single Co^II atom is located in a pseudo‐octahedral addendum site. Short‐lived states are observed for the two Co^III‐containing heteropolyanions 2 a (τ=4.4 ps) and 4 a (τ=6.3 ps) and assigned solely to O→Co^III charge transfer. The dramatically extended lifetime for 1 a versus 3 a is ascribed to a structural change permitted by the coordinatively flexible central site, weak orbital overlap of the central Co with the polytungstate framework, and putative transient valence trapping of the excited electron on a single W atom, a phenomenon not noted previously in POMs.