Bond isomerism, formation of heterocyclic cationic complex, and insertion into the tantalum-fluorine bond in the reaction of TaF5 with MeNCO in CH2Cl2
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
Authors: Il'in, E. G.; Ovchinnikova, N. A.; Ignatov, M. E.
Abstract
The reaction of tantalum pentafluoride with methyl isocyanate in dichloromethane was studied by F-19 NMR and IR spectroscopy. The reaction was found to give bond isomers TaF5L, in which methyl isocyanate (L) is coordinated in the monodentate mode via N or O atom, and the heterocyclic cation [(mu-F)(mu-MeNCO)(TaF4)(2)] (n) (+) (n=1,2). On storage of the reaction mixture, a signal in the C-F bond region appears in the spectrum and other new signals appear, which were assigned to the formation of O- and N- bonded isomers of pentafluoro complex of tantalum with aminocarboxylic acid fluoride anions [FC(O)N(Me)TaF5](-) and [N{Me)C(F)OTaF5](-), which can be considered as insertion of MeNCO into the Ta-F bond. The IR spectroscopy data support these assumptions.
Tantalum(V) fluoride complexes of thio- and seleno-ether ligands and a comparison with the TaX5 (X = Cl or Br) analogues
JOURNAL OF FLUORINE CHEMISTRY
Authors: Benjamin, Sophie L.; Hyslop, Alison; Levason, William; Reid, Gillian
Abstract
Reaction of TaF5 with SMe2 and RS(CH2)(2)SR (R = Me, Et or Pr-i) in anhydrous CH2Cl2 solution produce colourless, extremely moisture sensitive crystals of [TaF4(SMe2)(4)][TaF6] and [TaF4{RS(CH2)(2)SR}(2)][TaF6] respectively, which contain eight-coordinate cations and octahedral anions, whereas TaF5 reacts with neat SR2 (R = Me or Et) to form six-coordinate [TaF5(SR2)]. Very unstable [TaF5(SeMe2)] and [(TaF5)(2){mu-MeSe(CH2)(2)SeMe}] were isolated with the selenoether ligands and also contain six-coordinate tantalum species. Selected complexes of TaCl5 and TaBr5 have been prepared for comparison. The complexes have been characterised by IR, UV/visible and H-1 and F-19{H-1} NMR spectroscopies, and X-ray crystal structures are reported for [TaF4{MeS(CH2)(2)SMe}(2)][TaF6], [(TaCl5)(2){mu-MeSe(CH2)(2)SeMe}] and [TaCl5(SeMe2)]. O 2012 Elsevier B.V. All rights reserved.