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Persistent URL http://purl.org/net/epubs/work/66494
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Record Id 66494
Title Simulating the pyrolysis of polyazides: a mechanistic case study of the [P(N3)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.
Organisation CSE-CMSG , STFC , SCI-COMP
Keywords Chemistry
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Language English (EN)
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Journal Article Inorg Chem 52, no. 4 (2013): 1747-1754. doi:10.1021/ic301178h 2013