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Contrasting electronic requirements for CH binding and CH activation in d 6 half‐sandwich complexes of rhenium and tungsten
Author(s) -
Thenraj Murugesan,
Samuelson Ashoka G.
Publication year - 2015
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24002
Subject(s) - rhenium , chemistry , alkane , reactivity (psychology) , carbene , density functional theory , metal , ligand (biochemistry) , carbon monoxide , tungsten , electron transfer , metal carbonyl , photochemistry , computational chemistry , catalysis , inorganic chemistry , organic chemistry , medicine , biochemistry , alternative medicine , receptor , pathology
A computational study of the interaction half‐sandwich metal fragments (metal = Re/W, electron count = d 6 ), containing linear nitrosyl (NO + ), carbon monoxide (CO), trifluorophosphine (PF 3 ), N ‐heterocyclic carbene (NHC) ligands with alkanes are conducted using density functional theory employing the hybrid meta‐GGA functional (M06). Electron deficiency on the metal increases with the ligand in the order NHC < CO < PF 3 < NO + . Electron‐withdrawing ligands like NO + lead to more stable alkane complexes than NHC, a strong electron donor. Energy decomposition analysis shows that stabilization is due to orbital interaction involving charge transfer from the alkane to the metal. Reactivity and dynamics of the alkane fragment are facilitated by electron donors on the metal. These results match most of the experimental results known for CO and PF 3 complexes. The study suggests activation of alkane in metal complexes to be facile with strong donor ligands like NHC. © 2015 Wiley Periodicals, Inc.