Lewis acid behavior of ReO{sub 2}F{sub 3}: Synthesis of (ReO{sub 2}F{sub 3}){sub {infinity}}, ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, Re{sub 3}O{sub 6}F{sub 10}{sup {minus}}, and ReO{sub 2}F{sub 3}(CH{sub 3}CN) and study by NMR spectroscopy, Raman spectroscopy, and density functional theory calculations; and X-ray structures of [Li][ReO{sub 2}F{sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{sub 3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN
- McMaster Univ. Hamilton, Ontario (Canada). Dept. of Chemistry
- Pacific Northwest National Lab., Richland, WA (United States). William R. Wiley Environmental Molecular Sciences Lab.
The reaction of Re{sub 2}O{sub 7} with XeF{sub 6} in anhydrous HF provides a convenient route to high-purity ReO{sub 2}F{sub 3}. The fluoride acceptor and Lewis base properties of ReO{sub 2}F{sub 3} have been investigated leading to the formation of [M][ReO{sub 2}F{sub 4}] [M = Li, Na, Cs, N(CH{sub 3}){sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{sub 3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 2}F{sub 3}(CH{sub 3}CN). The ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, and Re{sub 3}O{sub 6}F{sub 10{sup {minus}} anions and the ReO{sub 2}F{sub 3}(CH{sub 3}CN) adduct have been characterized in the solid state by Raman spectroscopy, and the structures [Li][ReO{sub 2}F{sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{approximately}3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN have been determined by X-ray crystallography. The structure of ReO{sub 2}F{sub 4}{sup {minus}} consists of a cis-dioxo arrangement of Re-O double bonds in which the Re-F bonds trans to the oxygen atoms are significantly lengthened as a result of the trans influence of the oxygens. The Re{sub 2}O{sub 4}F{sub 7}{sup {minus}} and Re{sub 3}O{sub 6}F{sub 10}{sup {minus}} anions and polymeric ReO{sub 2}F{sub 3} are open chains containing fluorine-bridged ReO{sub 2}F{sub 4} units in which each pair of Re-O bonds are cis to each other and the fluorine bridges are trans to oxygens. The trans influence of the oxygens is manifested by elongated terminal Re-F bonds trans to Re-O bonds as in ReO{sub 2}F{sub 4}{sup {minus}} and by the occurrence of both fluorine bridges trans to Re-O bonds. Fluorine-19 NMR spectra show that ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, and ReO{sub 2}F{sub 3}(CH{sub 3}CN) have cis-dioxo arrangements in CH{sub 3}CN solution. Density functional theory calculations at the local and nonlocal levels confirm that the cis-dioxo isomers of ReO{sub 2}F{sub 4}{sup {minus}} and ReO{sub 2}F{sub 3}(CH{sub 3}CN), where CH{sub 3}CN is bonded trans to an oxygen, are the energy-minimized structures. The adduct ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN was obtained by hydrolysis of ReO{sub 2}F{sub 3}(CH{sub 3}CN), and was shown by X-ray crystallography to have a facial arrangement of oxygen atoms on rhenium.
- Sponsoring Organization:
- Natural Sciences and Engineering Research Council of Canada, Ottawa, ON (Canada); Petroleum Research Fund (United States); National Science Foundation, Washington, DC (United States); USDOE, Washington, DC (United States)
- DOE Contract Number:
- AC06-76RL01830
- OSTI ID:
- 354360
- Journal Information:
- Inorganic Chemistry, Vol. 38, Issue 10; Other Information: PBD: 17 May 1999
- Country of Publication:
- United States
- Language:
- English
Similar Records
Synthesis and characterization of rhenium thiolate complexes. Crystal and molecular structures of [NBu{sub 4}][ReO(H{sub 2}O)Br{sub 4}]{center_dot}2H{sub 2}O, [Bu{sub 4}N][ReOBr{sub 4}(OPPh{sub 3})], [ReO(SC{sub 5}H{sub 4}N){sub 3}], [ReO(SC{sub 4}H{sub 3}N{sub 2}){sub 3}][ReO(OH)(SC{sub 5}H{sub 4}N-3,6-(SiMe{sub 2}Bu{sup t}){sub 2}){sub 2}], [Re(N{sub 2}COC{sub 6}H{sub 5})(SC{sub 5}H{sub 4}N)Cl(PPh{sub 3}){sub 2}], and [Re(PPh{sub 3})(SC{sub 4}H{sub 3}N{sub 2}){sub 3}]
Synthesis and characterization by sup 1 H, sup 13 C, and sup 19 F NMR spectroscopy of (CH sub 3 CN) sub n (CO) sub 4 minus n (NO)W(. mu. -F)BF sub 3 and ((CH sub 3 CN) sub n+1 (CO) sub 4 minus n (NO)W)(BF sub 4 )(n = 0 minus 2), tungsten mononitrosyl carbonyl cations with labile acetonitrile and ((. mu. -F)BF sub 3 ) sup minus ligands