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Modulation of Metal Carbonyl Stretching Frequencies in the Second Coordination Sphere through the Internal Stark Effect
Author(s) -
Parker Gemma L.,
Van Lommel Ruben,
Roig Nil,
Alonso Mercedes,
Chaplin Adrian B.
Publication year - 2022
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/chem.202202283
Subject(s) - rhodium , chemistry , stark effect , coordination sphere , ruthenium , octahedron , metal carbonyl , crystallography , electric field , metal , photochemistry , stereochemistry , catalysis , crystal structure , organic chemistry , physics , quantum mechanics
Spectroscopic and computational examination of a homologous series of rhodium(I) pybox carbonyl complexes has revealed a correlation between the conformation of the flanking aryl‐substituted oxazoline donors and the carbonyl stretching frequency. This relationship is also observed experimentally for octahedral rhodium(III) and ruthenium(II) variants and cannot be explained through the classical, Dewar–Chatt–Duncanson, interpretation of metal‐carbonyl bonding. Instead, these findings are reconciled by local changes in the magnitude of the electric field that is projected along the metal‐carbonyl vector: the internal Stark effect.