Simulating the pyrolysis of polyazides: a mechanistic case study of the [[P(N3)6]- anion.
Pyrolysis of the homoleptic azido complex [P(N(3))(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(N(3))(5)] is fluxional and engages in pseudorotation via a Berry mechanism.
Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, UK. carmen.domene@chem.ox.ac.uk
Carmen
C
Domene
Peter
P
Portius
Patrick W
PW
Fowler
Leonardo
L
Bernasconi