Two series of oxo-bridged Co(III) complexes of the type Co(4)O(4)(O(2)CC(6)H(4)-X)(4)(py)(4) (1) and Co(4)O(4)(O(2)CC(6)H(4)-X)(4)(4-Mepy)(4) (2), where X = H (a), Me (b), MeO (c), Cl (d), NO(2) (e), have been synthesized and characterized in detail. The molecular structures of the complexes consist of a cubelike Co(4)(mu(3)-O)(4) core having Co and O atoms at alternate vertices with carboxylato ligands bridging the Co(3+) ions along four face diagonals of the approximate cube. Nitrogen atoms from pyridyl ligands complete the distorted-octahedral coordination around each Co(III). These neutral Co(III) complexes undergo a nearly reversible one-electron oxidation involving the redox couple [Co(4)(III)(mu(3)-O)(4)](4+) <--> [Co(3)(III)Co(IV)(mu(3)-O)(4)](5+) at potentials (approximately 0.7-1.0 V) that linearly depend on the electronic influence of X. The cobalt(III) clusters of types 1 and 2 have been found to effectively promote the TBHP oxidation of benzylic alcohols under homogeneous conditions to produce the corresponding carbonyl compounds.
The study presents a quantitative estimation of B-H b Á Á Áπ interaction in diboranelocalized-π half sandwiches and sandwiches. DFT-D3 method is used for geometry optimization and estimating the stability of the complexes (in terms of stabilization energies). The diborane molecule is the source of bridging hydrogen and O 2 , C 2 H 4 , and C 2 H 2 molecules are considered as the localized π-systems. MP2 and CCSD(T) calculations are also performed to measure the stability of the chosen complexes. Results indicate that the complexes are feebly stable in gas phase with stabilization energies <5.0 kcal mol −1 . Compared to DFT-D3 functionals, MP2 calculations are found to be more suitable in predicting the stability of the complexes. Dispersive interaction is the primary mode of interaction in stabilizing the complexes. Presence of substituents either on diborane or on the considered π-systems play key role in stabilizing the complexes. Thermochemical analysis demonstrates the exothermic nature of complexation. 1 H and 13 B NMR analysis are also performed. K E Y W O R D S B-H b Á Á Áπ interaction, CCSD(T), DFT-D3, dispersion interaction, MP2, sandwich
Effect of doping B and/or N on the reactivity, aromaticity and absorption spectra of graphene and functionalized (–OH and –COOH) carbon cluster mimicking graphene is studied using DFT, DFRT and TD-DFT.
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