Using ab initio Gaussian self-consistent field (SGF) and configuration-interaction (Cl) methods, the geometry, binding energy, and dipole moment are obtained for ONF and NOF. It is found that only Cl methods lead to agreement with the experimental NF bond distance of ONF. The optimized geometry for NOF is 1.07 Á for the N-0 and 1.76 Á for the O-F bond distance, with a bond angle of 112.3°. Basis sets with polarization functions are required to obtain a positive atomization energy for ONF. Population analysis data show both molecules to be of polar structure. The molecular orbital and natural orbital contributions to the N-F bond of ONF (and O-F bond of NOF) are studied.

. Can. J. Chem. 67, 1501 (1989).The hydrolysis of TeF5CI has been followed by '25Te and ' 9~ NMR spectroscopy. The spectra show that the known series (HO),TeF6-, (n = 2-6) are present. In addition the spectra are consistent with the presence of the previously unreported series (HO),TeF5-,Cl (n = 1-3) as well as unidentified fluorotellurium(1V) species. Evidence is presented for the new species trans-and cis-HOTeF4C1 and cis, mer-(HO)2TeF3C1. The course of the hydrolysis of TeF5Cl is compared with that of SF5Cl.Key words: trans-tetrafluorotellurium hydroxychloride, cis-tetrafluorotellurium hydroxychloride, cis,mer-tetrafluorotellurium dihydroxychloride, pentafluorotellurium chloride, hydrolysis. LAWRENCE J. LAWLOR, ALBAN MARTIN, MICHAEL P. MURCHIE, JACK PASSMORE et JEREMY C. P. SANDERS. Can. J. Chem. 67, 1501 (1989).Faisant appel a la RMN du 125Te et du 1 9~, on a suivi I'kvolution de la rtaction d'hydrolyse du TeF5CI. Les spectres dkmontrent que les produits connus de la skrie (0H),TeF6-,, (n = 2-6) sont prksents. De plus, les spectres sont en accord avec la prtsence des produits de la strie (OH),TeF5-"Cl (n = 1-3) qui n'avaient pas t t t rapportts antkrieurement ainsi que d'esptces non-identifikes de fluorotellure(1V). On prtsente des donnkes relatives aux nouvelles espkces trans-et cis-HOTeF4C1 ainsi que ~is,mer-(HO)~TeF~Cl. On compare l'hydrolyse du TeF5C1 avec celle du SF5C1.

No 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.

The reaction of TeClF5 with CH3OH, and CH3OSiMe3, leads to a mixture of cis- and trans-(CH3O)TeClF4 in a ratio of 1:6, as well as some unidentified Te(IV) product. The vibrational spectrum of the 1:6 mixture of cis- and trans-(CH3O)TeClF4 was accounted for on the basis of the predominant pseudo-C4vtrans isomer. TeClF5 is unreactive towards anhydrous HF, SbF5, AlCl3, SO2, F2, and ClF at room temperature. Over the temperature range 70–250 °C it thermally decomposes to TeF6, TeF4, and Cl2. It slowly reacts with CsF to form CsTeF5, TeF6, Cl2, and small amounts of ClF, and with HNMe2 it is also reduced to form TeF4•HNMe2.