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The gas-phase route from Cp*2P6 to neutral hexaphosphorus
Markus Reiher1, Detlef Schröder
1Lehrstuhl für Theoretische Chemie, Universität Erlangen-Nürnberg Egerlandstrasse 3, 91058 Erlangen, Germany. markus.reiher@chemie.uni-erlangen.de
Chemistry (Weinheim an Der Bergstrasse, Germany)
|February 4, 2003
Summary
Density functional theory explains hexaphosphorus (P6) formation from Cp*P6+ collisions. Unfavorable electron transfer and low dissociation energy favor P6 generation, highlighting Cp* as an excellent leaving group.
Area of Science:
- Computational Chemistry
- Inorganic Chemistry
- Quantum Mechanics
Background:
- Hexaphosphorus (P6) species are of interest in inorganic chemistry.
- Understanding the fragmentation and redox behavior of phosphorus-containing cations is crucial.
Purpose of the Study:
- To investigate the fragmentation and redox behavior of CpnP6+/0 and Cp*nP6+/0 species using density functional theory.
- To explain the experimental observation of neutral P6 formation from Cp*P6+ cation collisions.
Main Methods:
- Density functional theory (DFT) calculations were employed.
- Analysis of fragmentation pathways and redox potentials.
Main Results:
- DFT calculations predict unfavorable Franck-Condon factors for electron transfer to Cp*P6+, explaining its negligible contribution.
- Dissociation of Cp*P6+ into Cp*(+) + P6 has a low energy requirement, facilitating neutral P6 formation.
- Unsubstituted cyclopentadienyl ligands (Cp) are less effective than Cp* in promoting P6 generation.
Conclusions:
- The study provides a theoretical explanation for the efficient gas-phase generation of neutral P6.
- Cp* is confirmed as a particularly effective leaving group in these systems.