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Spontaneous Phosphorus‐Halogen Bond Cleavage in N ‐Heterocyclic Halogenophosphanes Revisited: The Case of P–Br and P–I Bonds
Author(s) -
Burck Sebastian,
Gudat Dietrich,
Nieger Martin,
Benkö Zoltan,
Nyulászi Lászlo,
Szieberth Denes
Publication year - 2009
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200800408
Subject(s) - chemistry , intramolecular force , halogen bond , lewis acids and bases , intermolecular force , bond cleavage , crystal structure , halogen , crystallography , ionic bonding , triiodide , stereochemistry , molecule , ion , organic chemistry , alkyl , catalysis , electrode , dye sensitized solar cell , electrolyte
P ‐bromo‐ and P ‐Iodo‐substituted N ‐heterocyclic phosphanes (NHP) were synthesized by halogen exchange starting from the P ‐chloro compound and characterized by spectroscopic data and X‐ray diffraction studies. Whereas the Br‐NHP still forms a molecular crystal, the solid‐state structure of the I‐derivative consists of ion‐pairs which assemble via secondary P···I interactions to form one‐dimensional coordination polymers. Computational studies indicate that the bond dissociation is due to a combination of intramolecular stabilisation (aromatisation of the phosphenium cation formed) and intermolecular Lewis‐acid/base interactions. Reaction of the I‐NHP with I 2 proceeded under complete P–I bond cleavage to give an ionic phosphenium triiodide whose single‐crystal X‐ray diffraction study revealed a unique supramolecular structure.