Experimental and Theoretical Vibrational Studies of Covalent X-N3 Azides (X = H, F, Cl, Br, I). Application of the Density Functional Theory and Comparison with ab Initio Results

Schulz, Axel; Tornieporth‐Oetting, Inis C.; Klapoetke, Thomas M.

doi:10.1021/ic00121a012

Cited by 47 publications

(31 citation statements)

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“…39 Generally, the agreement between the theoretical and experimental data for the heat of formation calculated at the MP2 level (DZ+P basis set) is very good for HN 3 . 40 This gives credence to those calculated dissociation energies for which there are no experimental data due to the extreme lability of the compounds in question.…”

Section: Structure and Bondingsupporting

confidence: 55%

Inorganic and Transition Metal Azides

Seok

Klapötke

2010

Bulletin of the Korean Chemical Society

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Experimental and theoretical studies show that all covalent azides possess a nonlinear azide group. They also rationalize this remarkable structural feature. We have seen that the most important non-covalent contributions in the covalently bound azides system (X-N1-N2-N3) are the π-delocalization over the entire molecule and a strong negative hyperconjugation which donates electron density from the filled σ (X-N1) orbital into the unfilled, antibonding π* (N2-N3) orbital. For transition metal azide complexes, a bent configuration and a small difference between the N-N bond lengths, generally the longer one being adjacent to the transition metal, were observed.

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Section: Structure and Bondingsupporting

confidence: 55%

Inorganic and Transition Metal Azides

Seok

Klapötke

2010

Bulletin of the Korean Chemical Society

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“…The assignment of the six normal vibrations can be made as follows: ~(tS-AtN3), ~,2(~-At--N3), ~3('y-N3), ~'4(t~-N3), .v5(~'s-N3), lJ6(~'as-N3) [4].…”

Section: Theoretical Structure Of Astatine Azidementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…The structures and vibrational data of all these azides (X = F, CI, Br, I) have been determined experimentally and theoretically [3,4]. It has been shown by us and others that electron-correlated ab initio computations at the MP2 level [3] as well as density functional calculations at the B-LYP level of theory [4] are very suitable to predict both the geometries as well as frequencies of these species. Moreover, the use of the pseudopotential method has proven to be very cpu-time-efficient [4] and superior to all-electron computations when quasirelativistic pseudopotentials (ECPs) of the semilocal type were applied, where the non-relativistic Hamiltonian was corrected (i) for the relativistic mass increase of the inner electrons and (ii) for the (averaged) spin-orbit coupling [5].…”

Section: Introductionmentioning

confidence: 99%

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The structure of astatine azide, AtN3—A theoretical study

Klapötke

Schulz

1997

Struct Chem

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For the first time theoretical evidence for the experimentally hitherto unknown astatine azide, AtN 3, the heaviest of all halogen azides, is presented. The structure and the vibrational data of AtN3 were computed ab initio at RHF and electron-correlated MP2 levels of theory using a quasirelativistic (MWB) pseudopotential for astatine, where the basis functions for the valence s and p electrons consist of the standard double-~" basis set. For nitrogen a standard 6-31G(d) basis was used. The molecule represents a true minimum (NIMAG = 0) at all levels of theory applied and is predicted to exist in a planar trans bent Cs structure. Since hybrid functionals, which define the exchange functional as a linear combination of Hartree-Fock, local, and gradient-corrected exchange terms, are known to predict the experimental parameters best, we also computed astatine azide (

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“…However, to get some detailed information about the molecular structures of these compounds, we decided to calculate the structures of the isolated covalent molecules at the semiempirical PM3 level of theory. Since the azide group can be regarded as a pseudohalogen [8], and the group electronegativity (v) of the N 3 radical was calculated to lie between the value for Cl and that for Br (v values in eV: Cl 8.3, Br 7.5, N 3 7.7 [9,10]), it is reasonable to assume that the molecular properties of P 3 N 3 (N 3 ) 6‫מ‬n R n compounds will be similar to those of their chlorine analogues P 3 N 3 Cl 6‫מ‬n R n . In the work presented in this article, we therefore chose the Cl compounds P 3 N 3 Cl 4 (NC 5 H 10 ) 2 (1a) and P 3 N 3 Cl 3 (NC 5 H 10 ) 3 (2a), which can easily be obtained in crystalline form, to determine their structures by X-ray diffraction methods and by semiempirical PM3 calculations.…”

Section: Introductionmentioning

confidence: 99%

The x-ray structure determinations and semiempirical PM3 calculations of two chloro(piperidyl)cyclotri(phosphazenes)

Klap��tke

White

1997

Heteroat. Chem.

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Single crystals of 2,4,6,6‐tetrachloro‐2,4‐bis(piperid‐yl)cyclotri(phosphazene) (1a) and of 2,4,6‐trichloro‐2,4,6‐tris(piperidyl)cyclotri(phosphazene) (2a) were grown from petroleum ether solution. The structures of both compounds were determined by single‐crystal X‐ray diffraction analyses. Compound 1a crystallizes in the monoclinic space group P 21/n with Z = 4 and unit cell dimensions a = 9.3994(4), b = 19.204(3), c = 11.5664(4) Å, and β = 108.718(4)°. Compound 2a crystallizes in the triclinic space group P 1 with Z = 4 and unit cell dimensions a = 12.8289(2), b = 13.8856(2), c = 14.63810(10) Å, and α = 100.7621(5), β = 91.0094(2), γ = 113.9757(6)°. The experimentally obtained structural parameters for the covalent molecules 1a and 2a compare well with those calculated at the semiempirical PM3 level of theory. These results give credence to the PM3 calculated structures of 2,4,6,6‐tetraazido‐2,4‐bis(piperidyl)cy‐clotri(phosphazene) (1b) and 2,4,6‐triazido‐2,4,6‐tris(piperidyl)cyclotri(phosphazene) (2b) for which presently there are no experimental data available. © 1997 John Wiley & Sons, Inc. Heteroatom Chem 8: 267–271, 1997.

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Experimental and Theoretical Vibrational Studies of Covalent X-N3 Azides (X = H, F, Cl, Br, I). Application of the Density Functional Theory and Comparison with ab Initio Results

Cited by 47 publications

References 1 publication

Inorganic and Transition Metal Azides

Inorganic and Transition Metal Azides

The structure of astatine azide, AtN3—A theoretical study

The x-ray structure determinations and semiempirical PM3 calculations of two chloro(piperidyl)cyclotri(phosphazenes)

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