Publication

Quantum Chemical Investigation of the Transition States and Intermediates for the Reaction of the Nitrosonium Ion with the Pentaammineazidocobalt(III) Ion

François Rotzinger
2016
Journal Articles

Abstract

The water exchange reaction on Co(NH3)(5)OH23+ was investigated with various density functionals and basis sets. A Gibbs activation energy (Delta G(double dagger)) agreeing with experiment was obtained with the long-range-corrected functionals omega B97X-D3 and LC-BOP-LRD, SMD hydration, and modified Karlsruhe def2-TZVP basis sets. This computational technique was then applied to the reaction of NO+ with Co(NH3)(5)N-3(2+). All of the possible pathways were investigated, NO+ attack at the terminal N of Co(NH3)(5)N-3(2+) via the E and the Z isomers of the transition states, and NO+ attack at the bound N of azide, also via both isomers. The most favorable pathway proceeds via the attack at the bound N via the Z isomer. This leads to the intermediate with an oxatetrazole ligand bound to Co (III) at the N in the 3-position, Co(NH3)(5)(cycl-N4O)(3+), which undergoes N-2 elimination to yield the Co(NH3)(5)NN2O3+ intermediate. The subsequent substitution of N2O by water follows the Id mechanism with retention of the configuration. No evidence for the existence of the square-pyramidal pentacoordinated intermediate Co(NH3)(5)(3+) was found. All of the investigated intermediates, Co(NH3)(5)N-2(3+), Co(NH3)(5)E-N(N-2) (NO), CO (NH3)(5)(E-ON4)(3+), CO(NH3)(5)ON23+, CO(NH3)(5)(cycl-N4O)(3+), and Co(NH3)(5)N2O3+, exhibit short lifetimes of less than similar to 60 mu s and react via the I-d mechanism.

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https://infoscience.epfl.ch/entities/publication/27f484db-5c4b-4497-916a-fbb04107da12

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François Rotzinger
2016
Journal Articles

Abstract

Official source

https://infoscience.epfl.ch/entities/publication/27f484db-5c4b-4497-916a-fbb04107da12

About this result

Related concepts (13)

Density functional theory

Density-functional theory (DFT) is a computational quantum mechanical modelling method used in physics, chemistry and materials science to investigate the electronic structure (or nuclear structure) (principally the ground state) of many-body systems, in particular atoms, molecules, and the condensed phases. Using this theory, the properties of a many-electron system can be determined by using functionals, i.e. functions of another function. In the case of DFT, these are functionals of the spatially dependent electron density.

Orthonormal basis

In mathematics, particularly linear algebra, an orthonormal basis for an inner product space V with finite dimension is a basis for whose vectors are orthonormal, that is, they are all unit vectors and orthogonal to each other. For example, the standard basis for a Euclidean space is an orthonormal basis, where the relevant inner product is the dot product of vectors. The of the standard basis under a rotation or reflection (or any orthogonal transformation) is also orthonormal, and every orthonormal basis for arises in this fashion.

Basis set (chemistry)

In theoretical and computational chemistry, a basis set is a set of functions (called basis functions) that is used to represent the electronic wave function in the Hartree–Fock method or density-functional theory in order to turn the partial differential equations of the model into algebraic equations suitable for efficient implementation on a computer. The use of basis sets is equivalent to the use of an approximate resolution of the identity: the orbitals are expanded within the basis set as a linear combination of the basis functions , where the expansion coefficients are given by .

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