Linear Chain Formation by an Oxovanadium(V) Complex of p-Methylhexahomotrioxacalix[3]arene.
The oxovanadium(V) complex 4 can be readily synthesized by the reaction of the lithium salt of p-methylhexahomotrioxacalix[3]arene trianion 3 with VOCl(3). Infrared spectra indicate a terminal V=O for complex 4 in solution and V=O.V dative interactions in the solid state consistent with the formation of a &mgr;-oxo-bridged linear chain polymer 1 (M = V, Y = O, X(3) = trianion of macrocycle 2a). Vanadium-51 NMR spectra indicate increased shielding for the linear chain polymer in the solid state compared to complex 4 in solution. Complex 4 and its linear chain polymer are proposed to have the oxovanadium group contained within the cup of the macrocycle ligand as shown in structures 5 and 7, respectively, where the cone represents macrocycle 2a.
Hampton
Philip D.
PD
Department of Chemistry and Center for Micro-Engineered Ceramics, University of New Mexico, Albuquerque, New Mexico 87131, and Materials Aging and Reliability, Bulk Properties Department, Sandia National Laboratories, Albuquerque, New Mexico 87185.
Daitch
Charles E.
CE
Alam
Todd M.
TM
Pruss
Eugene A.
EA