Mononuclear anionic AO sub(2)X sub(3) compounds with non-VSEPR structure

The molybdenyl compound [NBu sub(4)][MoO sub(2)(C sub(6)F sub(5)) sub(3)] (1) has been obtained by low-temperature treatment of MoO sub(2)Cl sub(2) with LiC sub(6)F sub(5) in Et sub(2)O followed by addition of [NBu sub(4)]Br. This compound of the (AO sub(2)X sub(3)) super(-) type shows an unusual fi...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2014-04, Vol.43 (20), p.7615-7621
Main Authors: Garcia-Monforte, MAngeles, Baya, Miguel, Betore, MPilar, Martin, Antonio, Menjon, Babil
Format: Article
Language:English
Subjects:
Exchange
Mathematical models
NMR spectroscopy
Stability
Tetrahedrons
Online Access:Get full text
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Summary:The molybdenyl compound [NBu sub(4)][MoO sub(2)(C sub(6)F sub(5)) sub(3)] (1) has been obtained by low-temperature treatment of MoO sub(2)Cl sub(2) with LiC sub(6)F sub(5) in Et sub(2)O followed by addition of [NBu sub(4)]Br. This compound of the (AO sub(2)X sub(3)) super(-) type shows an unusual five-coordinate structure not lying in the Berry-pseudorotation path: it can be described rather as an edge-capped tetrahedron (TE-5). The same kind of structure has been found by DFT calculations to be the most energetically favored for the mononuclear (MoO sub(2)X sub(3)) super( -) model species, where X = H, Cl or CN. Compound 1 exhibits marked stereochemical stability, as it shows no sign of exchange between chemically inequivalent C sub(6)F sub(5) groups even at 150 degree C in dmf solution ( super(19)F NMR spectroscopy).
ISSN:1477-9226
1477-9234
DOI:10.1039/c4dt00525b