Organofluorine binding to sodium and thallium(I) in molecular fluoroalkoxide compounds

Journal Article · Wed Jun 16 04:00:00 EDT 1993 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00065a021· OSTI ID:6258765

Samuels, J A; Lobkovsky, E B; Streib, W E; Folting, K; Huffman, J C; Zwanziger, J W; Caulton, K G ^[1]

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1. Indiana Univ., Bloomington (United States)

The compounds (NaOR[sub f])[sub 4] (R[sub f] = CH(CF)[sub 3])[sub 2], Zr(OR[sub f])[sub 4] (2), Zr(OR[prime][sub f])[sub 4] (R[prime][sub f] = CMe(CF[sub 3])[sub 2]) (3), Na[sub 2]Zr(OR[sub f])[sub 6](C[sub 6]H[sub 6])[sub n] (4a when n = 1 and 4b when n = 2), and Tl[sub 2]Zr(OR[sub f])[sub 6] (5) have been synthesized and characterized by IR, multinuclear NMR, and mass spectrometry and (for 1, 3, 4a, b, and 5) X-ray diffraction structure determinations. The heavy fluorination of the molecular periphery makes all of these molecular compounds highly volatile. In addition, all X-ray structures (except that of 3) show evidence of intramolecular ([open quotes]secondary[close quotes]) bonding interactions between numerous organofluorines and the electrophiles sodium or thallium. The benzene in both solid compounds 4 forms a [pi]-complex to sodium. The absence of benzene in 5 leads to additional intermolecular Tl-F interactions. The reality of these electrophile-F interactions is further supported by the fact that [sup 205]Tl and [sup 19]F NMR studies show Tl-F coupling of a magnitude consistent with direct bonding. Moreover, variable-temperature [sup 205]Tl and [sup 19]F NMR studies reveal facile migration of both Tl electrophiles over the entire periphery of the Zr(OR[sub f])[sub 6] octahedron. Cleavage of C-F bonds is evident in the electron impact mass spectra of these molecules, and especially from the fact that chemical vapor deposition of (NaOR[sub f])[sub 4] onto silica at 285 [degrees]C gives NaF, not Na[sub 2]O. These ground-state metal-organfluorine interactions appear to provide a facile reaction channel for rupture of the strong C-F bond. 58 refs., 8 figs., 8 tabs.

• OSTI ID: 6258765
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 115:12; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
ALKALI METAL COMPOUNDS
CHEMICAL COATING
CHEMICAL VAPOR DEPOSITION
COHERENT SCATTERING
CRYSTALLOGRAPHY
DATA
DEPOSITION
DIFFRACTION
EXPERIMENTAL DATA
FLUORINE COMPOUNDS
HALOGEN COMPOUNDS
INFORMATION
MAGNETIC RESONANCE
MASS SPECTROSCOPY
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
RESONANCE
SCATTERING
SODIUM COMPOUNDS
SPECTROSCOPY
SURFACE COATING
SYNTHESIS
THALLIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION
ZIRCONIUM COMPOUNDS