Existence of cesium salts of CO2F-, CO2F22- and NO2F2-

Abstract

NotesFour Raman-polarized bands appeared at 707, 646, 326, and 257 cm-' and are therefore al modes and are assigned by comparison with related molecules (SBrF5,10i11 MC1F512,13 (M = S, Se, Te)) as ul(al), v2(al), u3(a1), and ~q(a1). Three corresponding infrared bands occur at 648,330, and 248 cm-' with the 707-cm-' band presumably hidden under the intense 715-cm-I band. The depolarized band at 720 cm-I in the Raman with a strong counterpart in the infrared at 7 15 cm-' is readily assigned as v8(e). The low-frequency depolarized bands at 244 and 144 cm-' are assigned as ulo(e) and ull(e), respectively, by comparison with related molecules. The Raman band at 306 cm-' appears to have a counterpart in the infrared at 302 cm-' (sh) and can be assigned as u9(e). One of the bl modes, vg, is too low in intensity to be observed in similar m o l e~u l e s , '~~'~ and ~g(b2) is probably hidden under the strong 646-cm-' band.Those vibrations involving motions of the TeF5 part of the molecule are rather similar in frequency to those reported for TeC1F5.I2 The TeBr stretching frequency of the 257-cm-' (u4) band is similar to the highest TeBr stretch in TeBr414 (250 cm-l).Acknowledgment. We thank the National Research Council (Canada) for financial assistance and a postgraduate scholarship to L.L. We are indebted to E. K. Richardson and R. Kaiser for the I9F N M R spectra. Registry No. TeBrFS, 21975-45-1; bromine, 7726-95-6; fluorine, 7782-41-4.

Photolysis of matrix-isolated hydridotetracarbonylcobalt(I). Comparison of the probabilities of carbonyl loss with hydrogen atom loss

“…Equipment and procedures for studying matrices of HCo(CO)4 have been described previously.1 Positions of infrared bands are (2) Rest, A. J.; Turner, J. J. J. Chem. Soc., Chem.…”

Reaction between carbon dioxide and elementary fluorine

“…In the second step, it seems to form CF 2 (OF) 2 by passing through reactions (12) [18][19][20] shown in the following reactions must be formed:…”

Tetramethylammonium Fluoride: Fundamental Properties and Applications in C-F Bond-Forming Reactions and as a Base

“…For instance, the Seppelt group described in 1995 that anhydrous TMAF-and other ionic sources of "naked" fluoride, but not inorganic salts such as CsF or AgF-reacts spontaneously with carbon dioxide, both without solvent or dissolved in CH 2 F 2 and CF 3 CHFCF 3 , to generate fluorocarbonate insoluble solid salts ([FCO 2 − ]) 349 (Scheme 19a) [159]. Although the existence of the fluorocarbonate anion had only been previously postulated without conclusive experimental confirmation [160], the authors experimentally corroborated the identity of such salts by NMR, IR, and Raman spectroscopy. Furthermore, ab initio calculations indicated that the C-F bond in FCO 2 is very weak (∆H = −110 kJ/mol, d(C-F) = 144.6 pm for ([FCO 2 − ]) (e.g.…”