Simulating the Pyrolysis of Polyazides: a Mechanistic Case Study of the [P(N-3)(6)](-) Anion

Carmen Domene Nunez, Peter Portius, Patrick W. Fowler, Leonardo Bernasconi

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Pyrolysis of the homoleptic azido complex [P(N3)6]− was simulated using density functional theory based molecular dynamics and analyzed further using electronic-structure calculations in atom-centered basis sets to calculate the geometries and electronic structures. Simulations at 600 and 1200 K predict a thermally induced and, on the simulation time scale, irreversible dissociation of an azido anion. The ligand loss is accompanied by a barrierless (free-energy) transition of the geometry of the complex coordination sphere from octahedral to trigonal bipyramidal. [P(N3)5] is fluxional and engages in pseudorotation via a Berry mechanism.
Original languageEnglish
Pages (from-to)1747-1754
Number of pages8
JournalInorganic Chemistry
Volume52
Issue number4
DOIs
Publication statusPublished - 1 Feb 2013

Keywords

  • SPACE GAUSSIAN PSEUDOPOTENTIALS, THERMAL-DECOMPOSITION, METHYL AZIDE, GAS-PHASE, AB-INITIO, STRUCTURAL-CHARACTERIZATION, MOLECULAR-DYNAMICS, CRYSTAL-STRUCTURE, ETHYL AZIDE, THIN-FILMS

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