The Raman and infra-red spectra of sulphur tetrafluoride

Dodd, R. E.; Woodward, L. A.; Roberts, H. L.

doi:10.1039/tf9565201052

Cited by 75 publications

(18 citation statements)

References 4 publications

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“…I-Iunt and Wilson (2) have assigiled a frequency of 274 cin-l, which they observed in the infrared spectruill of SO2F2, to the SF2 bending mode by coinparisoil with a frequency of 235 cm-1 in the spectrum of sulphur tetrafluoride, which has been assigiled as an S F bellding mode (9). I t seeills to us inore probable that this low frequency of 236 cm-I in the Rainan spectrum of liquid SF4 is due t o soine polymeric species formed by fluorine bridging between S F 4 molecules in the same way that ailtiinoily peiltafluoricle is associated by fluorine-bridge bonds (28).…”

Section: Sulphuryl Chloride and Szilphuryl Fluoridementioning

confidence: 99%

The Vibrational Spectra of Sulphuryl and Thionyl Halides

Gillespie¹,

Robinson²

1961

Can. J. Chem.

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New assignll~ents are proposed for the fundamental frequencies of SOF2, SOCIZ, SO2ClZ, S02F2, and SOzFBr, based on new measurements of the Raman spectrum of SOzClz and previous measurements of the infrared and Raman spectra of these molecules. The fundamental frequencies of these molecules are found to be related to each other and to those of similar lnolecules when the normal modes are described in terms of characteristic vibrations of the SO, SO?, S(Hal), and S(Hal)2 groups. INTRODUCTIONThe purpose of this paper is to give a consistent assignment of the observed vibrational frequencies of the thionyl and sulphuryl halides to the various modes of vibration of these molecules. This work was undertaken as a necessary preliminary to the interpretation of the vibrational spectra of a number of more complicated polysulphuryl compounds (1). Although both the infrared and Raman spectra of several of these molecules have each been examined a number of times, no complete agreement has been reached concerning the assignments of the observed frequencies (e.g. references 2, 3, and 4). We have found, by comparing the spectra of these n~olecules and certain others containing SO, SOz, S(I-Ial), and S(Ha1)Z groups, that a consistent and satisfactory set of assignments can be given for all the sulphuryl and thionyl halides that have been studied.Of the spectra discussed, only the Raman spectrum of SOzClz has been re-examined in the present work. The spectrum is shown in Fig. 1 sulphuryl chloride and for the other sulphuryl and thionyl halides obtained in the present and previous work are given in Tables I-V. ' iMa?zzrscript received illny 15, 1961. Colztribzrtion from the

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Section: Sulphuryl Chloride and Szilphuryl Fluoridementioning

confidence: 99%

The Vibrational Spectra of Sulphuryl and Thionyl Halides

Gillespie¹,

Robinson²

1961

Can. J. Chem.

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“…The steric effect of the nonbonding electron pair is evident in the molecular structure of both arsenic trifluoride (6) and seleniuln tetrafluoride (7). A similar steric influence is evidently responsible for the absence in the difluoride of the hexagonal (low quartz) and tetragonal (rutile) arrangements found (8,9) in the two forms of germanium dioxide.…”

Section: Discussion and Resultsmentioning

confidence: 65%

The Preparation and Some Properties of Germanium Difluoride

Bartlett¹,

Yu²

1961

Can. J. Chem.

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Germanium difluoride can be prepared by the reduction of germanium tetrafluoride with germani~im metal. I t is a white solid, n1.p. 110°, and is orthorhombic, a = 8.30, b = 5.17, c = 4.67 A. It possesses strong reducing properties. INTRODUCTIONEvidence for the existence of germa~lium difluoride was noted by Wiilltler (I), who heated potassiuin fluorogermanate in a strean1 of hydrogen and obtained a dark-colored mass, an aqueous extract of which yielded germanous sulphide with hydrogen sulphide. The only other description of a difluoride of germanium is that given by Dennis and Laubengayer (2) and it is their findings which are widely quoted. They characterized the fluoride as a white, sublimable, hygroscopic solid which disproportionated on heating. An aqueous solution of i t possessed the reducing properties of divalent gerinaniuin but the identity of the solid was not established by analysis.We have prepared inaterial similar to the latter and have proved it to be germanium difluoride. Seine of the physical and chemical properties of the compound have also been examined. DISCUSSION AND RESULTSDennis and Laubengayer prepared the difluoride by passing the gaseous tetrafluoride, produced by the pyrolysis of barium hexafluorogern~anate, over powdered germanium, above 100". We repeated this procedure and undoubtedly gerinaniuin difluoride was formed, but on no occasion was a sufficiently large or pure sample secured for analysis. The difluoride prepared in this way could not be transferred by distillation nor by pouring of the melt, without extensive interaction with the glass and disproportionation. These difficulties were associated with the presence of impurities, including water and hydrogen fluoride, as was inanifest from the etching of the glass apparatus and inay account for the delay in substantiating the earlier reports of the difluoride.When gern~anium tetrafluoride was used which had been prepared by the direct fluorination of germanium metal, under strictly anhydrous conditions, the reduction proceeded smoothly and extensively in the temperature range 150-300" and in this way gram samples of the con~pound could be prepared and transferred without decomposition.The stoichiometry, GeF2, was established by germanium and fluorine analysis and the divalency was confirmed by iodine titration.The white solid, 1n.p. 110°, distills without decomposition in vacz~o a t temperatures slightly above the fusion point. At higher temperatures disproportionation begins, as indicated by the appearance of an orange-red solid together with the concurrent evolution of gerinanium tetrafluoride. With soine sainples the temperature of decomposition was above 160" but since the decoinposition is evidently catalyzed by iinpurities it is possible that more thermally stable material than this can be made. As the temperature is raised the orange-red product becomes red-brown and finally black, the last being associated 1Manzlscript received Azc,oztst 18, 1960.

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“…However, this is literally a three-component system consisting of SF4, some free BFa, and the BF 3 -SF 4 complex. The significant observations here are the presence of a single resonance, a shift from the normal position of the SF4 resonance, the absence of the BF3 resonance or a resonance that might be attributed to the BF a -SF 4 complex, and the absence of the 33S-19F SF 4 satellites.…”

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confidence: 93%

“…Another new observation bears on the mechanism of fluorine exchange in SF 4 • In SF 6 the 19F spectrum consists of a single strong line representing the 32SF 6 resonance. Also readily discernible is a weak quartet arising from the 33SF 6 molecules (33S possesses a spin of !).…”

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confidence: 99%