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The Gas‐Phase Route from Cp* 2 P 6 to Neutral Hexaphosphorus
Author(s) -
Reiher Markus,
Schröder Detlef
Publication year - 2002
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20021202)8:23<5501::aid-chem5501>3.0.co;2-i
Subject(s) - gas phase , fragmentation (computing) , dissociation (chemistry) , chemistry , cyclopentadienyl complex , density functional theory , bond dissociation energy , electron transfer , atomic physics , chemical physics , computational chemistry , physics , organic chemistry , catalysis , computer science , operating system
Density functional theory has been applied to gain insight into the fragmentation and redox behavior of Cp n P 6 +/0 and Cp* n P 6 +/0 cations and neutral species ( n =1, 2) in the gas phase. Particular attention is paid to the previously reported generation of neutral hexaphosphorus upon high‐energy collisions of the Cp*P 6 + cation. Theory provides an explanation for the experimentally observed effect that collisional electron transfer to the Cp*P 6 + cation is negligible in that the associated Franck–Condon factors are predicted to be unfavorable. In contrast, dissociation of Cp*P 6 + into Cp* + +P 6 has a relatively low energy demand, thereby accounting for the efficient formation of neutral P 6 in the gas phase. Theoretical exploration of the parent compound Cp 2 P 6 reveals that the unsubstituted cyclopentadienyl ligand is much less suitable in this respect, thereby sustaining the previous suggestion that Cp* is a particularly good leaving group.