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Electronic coupling between molybdenum and tungsten quadruple bonds in molecular squares and extended chains linked by oxalate, acetylenedicarboxylate, and perfluoroterephthalate bridges
Author(s) -
Bursten Bruce E.,
Chisholm Malcolm H.,
Hadad Christopher M.,
Li Jun,
Wilson Paul J.
Publication year - 2002
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1560/6820-jh3k-ea64-9tt6
Subject(s) - chemistry , molybdenum , oxalate , tungsten , coupling (piping) , crystallography , computational chemistry , inorganic chemistry , organic chemistry , metallurgy , materials science
The electronic structures of dicarboxylate‐bridged complexes containing dimolybdenum and ditungsten quadruple bonds have been investigated using density function theory (gradient corrected and time‐dependent), which reveals the consequences of strong mixing of M 2 δ and oxalate π orbitals within extended chains and cyclic structures. Where the bridge is oxalate, acetylene dicarboxylate, and perfluoroterephthalate (PFT), the M 2 centers are in all cases strongly coupled through M 2 δ to bridge π‐conjugation. In the case of the chain compounds, this is strongly mediated by torsion angles along the chain. For the squares, only when the bridge is PFT is there a dependence on the orientation of the phenyl ring.