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Nitrido Dimers and Trimers of Tungsten Supported by t BuMe 2 SiO and CF 3 Me 2 CO Ligands, Respectively. Factors Influencing the Reductive Cleavage of Nitriles by Tungsten–Tungsten Triple Bonds and An Analysis of the Structure of the Cyclotrimer
Author(s) -
Chisholm Malcolm H.,
Folting Kirsten,
Lynn Matthew L.,
Tiedtke Darin B.,
Lemoigno Fréderic,
Eisenstein Odile
Publication year - 1999
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/(sici)1521-3765(19990802)5:8<2318::aid-chem2318>3.0.co;2-g
Subject(s) - pseudorotation , tungsten , chemistry , crystallography , reductive elimination , ring (chemistry) , cleavage (geology) , planar , triple bond , planarity testing , stereochemistry , computational chemistry , double bond , materials science , polymer chemistry , organic chemistry , catalysis , fracture (geology) , composite material , computer graphics (images) , computer science
The reductive cleavage of ArC≡N in the reaction with W 2 (OCMe 2 CF 3 ) 6 yields a novel trimeric compound [(CF 3 Me 2 CO) 3 WN] 3 (see diagram) with alternating long and short W−N bonds within a planar six‐membered ring. DFT calculations on [(OH) 9 W 3 N] 3 show that the origin of the short–long WN distances is associated with a local property of the pentacoordinated W. Calculations also show that unlike other pentacoordinated systems, pseudorotation at each W is difficult, leading to a high barrier for the interconversion of the long (axial) and short (equatorial) bonds.