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Nitrido Dimers and Trimers of Tungsten Supported by tBuMe2SiO and CF3Me2CO Ligands, Respectively. Factors Influencing the Reductive Cleavage of Nitriles by Tungsten-Tungsten Triple Bonds and An Analysis of the Structure of the Cyclotrimer
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1999
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EngineeringPentacoordinated W. CalculationsMolecular BiologyChemistryInorganic CompoundTungsten SupportedShort W−n BondsStructure ElucidationMaterials ScienceInorganic ChemistryTungsten-tungsten Triple BondsChemical BondNitrido DimersDft CalculationsMolecular ChemistryInorganic SynthesisNatural SciencesCoordination ComplexMolecular Complex
The reductive cleavage of ArC≡N in the reaction with W2(OCMe2CF3)6 yields a novel trimeric compound [(CF3Me2CO)3WN]3 (see diagram) with alternating long and short W−N bonds within a planar six-membered ring. DFT calculations on [(OH)9W3N]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.