Simulating the Pyrolysis of Polyazides: a Mechanistic Case Study of the [P(N3)6]鈭?/sup> Anion
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- 作者：Carmen Domene ; Peter Portius ; Patrick W. Fowler ; Leonardo Bernasconi
- 刊名：Inorganic Chemistry
- 出版年：2013
- 出版时间：February 18, 2013
- 年：2013
- 卷：52
- 期：4
- 页码：1747-1754
- 全文大小：437K
- 年卷期：v.52,no.4(February 18, 2013)
- ISSN：1520-510X
文摘
Pyrolysis of the homoleptic azido complex [P(N3)6]鈭?/sup> 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.