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

doi:10.1021/ic301178h

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

3 Citations (SciVal)

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 language	English
Pages (from-to)	1747-1754
Number of pages	8
Journal	Inorganic Chemistry
Volume	52
Issue number	4
DOIs	https://doi.org/10.1021/ic301178h
Publication status	Published - 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

UN SDGs

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10.1021/ic301178h

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

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.",

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author = "{Domene Nunez}, Carmen and Peter Portius and Fowler, {Patrick W.} and Leonardo Bernasconi",

year = "2013",

month = feb,

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doi = "10.1021/ic301178h",

language = "English",

volume = "52",

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journal = "Inorganic Chemistry",

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T1 - Simulating the Pyrolysis of Polyazides: a Mechanistic Case Study of the [P(N-3)(6)](-) Anion

AU - Domene Nunez, Carmen

AU - Portius, Peter

AU - Fowler, Patrick W.

AU - Bernasconi, Leonardo

PY - 2013/2/1

Y1 - 2013/2/1

N2 - 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.

AB - 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.

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

UR - http://dx.doi.org/10.1021/ic301178h

U2 - 10.1021/ic301178h

DO - 10.1021/ic301178h

M3 - Article

SN - 0020-1669

VL - 52

SP - 1747

EP - 1754

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 4

ER -

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

Abstract

Keywords

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