Electronic and molecular structure of pentafluorooxotellurate(1

Salts of the OTeF/sub 5//sup /minus// anion were investigated by ir and Raman spectroscopy and by x-ray crystallography. Experimental results were compared with ab initio Hartree-Fock calculations on the OTeF/sub 5/ radical, Na/sup +/OTeF/sub 5//sup /minus//, and the singlet and triplet states of the free OTeF/sub 5//sup /minus//. The compound ((PS)H/sup +/)(OTeF/sub 5//sup /minus//) was examined by single-crystal X-ray crystallography ((PS)H/sup +/ = protonated 1,8-bis(dimethylamino)naphthalene): /bar P/1, a = 8.241 (1) /angstrom/, b = 8.768 (2) /angstrom/, c = 12.591 (3) /angstrom/, /alpha/ = 74.08 (2)/degree/, /beta/ = 78.00 (2)/degree/, /gamma/ = 80.23 (2)/degree/, Z = 2, T = /minus/106/degree/C. Unlike other salts of the OTeF/sub 5//sup /minus// anion, ((PS)H/sup +/)(OTeF/sub 5//sup /minus//) did not exhibit any O/F disorder. Since the spectroscopic data for ((PS)H/sup +/)(OTeF/sub 5//sup /minus//) closely matched those of (N(n-Bu)/sub 4//sup +/)(OTeF/sub 5//sup /minus//), it was concluded that this structure contains the best approximation of the structure of the free OTeF/sub 5//sup /minus// anion. The librationally corrected results are Te-O = 1.803 /angstrom/, Te-F/sub ax/ = 1.872 /angstrom/, Te-F/sub eq/ = 1.870 /angstrom/ (average), and O-Te-F/sub eq/ = 95.2/degrees/ (average). A normal-coordinate analysis of OTeF/sub 5//sup /minus// was carried out by using this geometry and spectroscopic datamore » for the /sup 16/O and /sup 18/O equivalents of (N(n-Bu)/sub 4//sup +/)(OteF/sub 5//sup /minus//). 41 references, 5 figures, 8 tables.« less