The Raman spectra of tetrachloroantimony(V) dichloro nonafluorodiantimonate(V), tetrachloroantimony(V) undecafluoroantimonate(V), and related molecules

Abstract

The Raman spectra of [SbCl4+][Sb2Cl2F9−], [SbCl4+][Sb2F11−], [AsCl4+][SbF6−], and SbCl4F(NbF5)x are reported. The spectra of all compounds except the last are interpreted in terms of a tetrahedral cation with weak association between the cation and anion. The spectra of the adduct found between SbCl4F and NbF5 are interpreted in terms of polymeric fluorine bridged arrangements.

Tetrachloro- and Tetrabromoarsonium(V) Cations: Raman and 75As, 19F NMR Spectroscopic Characterization and X-ray Crystal Structures of [AsCl4][As(OTeF5)6] and [AsBr4][AsF(OTeF5)5]

“…The Sb−Cl stretching and Cl−Sb−Cl bending modes of the mixed Cl/OTeF 5 antimony(V) anions have not been explicitly assigned, but bands that compare favorably with their counterparts in the SbCl 4 - and SbCl 6 - anions 54 are indicated in Table (also see sections on syntheses and NMR spectra). The assignments of the AsCl 4 + and AsBr 4 + cation vibrations were made by comparison with the vibrational spectra of [AsX 4 ][AsF 6 ] (X = Cl, Br), ,, [AsCl 4 ][SbF 6 ], [AsCl 4 ][MCl 4 ] (M = Al, Ga), and [AsBr 4 ][Al 2 Br 7 ] 43 and were confirmed by theoretical calculations (see Computational Results and Table ). Splittings arising from the 35/37 Cl isotope effect, which were not reported in previous studies, were, however, observed on ν 1 (A 1 ) and ν 3 (T 2 ) of the AsCl 4 + cation for both the As(OTeF 5 ) 6 - and Sb(OTeF 5 ) 6 - n Cl n - salts, although they were better resolved in the latter case.…”

“…All members of the AsX 4 + (X = F, Cl, Br, I) series have been synthesized − and characterized by Raman spectroscopy, − and AsF 4 + 44 and AsCl 4 + 36 have also been characterized by infrared spectroscopy. The salts of AsF 4 + and AsCl 4 + , namely, [AsF 4 ][PtF 6 ], [AsCl 4 ][SbCl 6 ]·AsCl 3 , [AsCl 4 ][AsF 6 ], ,, [AsCl 4 ][AlCl 4 ], and [AsCl 4 ][GaCl 4 ] 35,40 are stable compounds, but only [AsCl 4 ][SbCl 6 ]·AsCl 3 45 and [AsCl 4 ][AsF 6 ] 46,47 have been structurally characterized by single-crystal X-ray diffraction.…”

Experimental and Theoretical Characterization of Cationic, Neutral, and Anionic Binary Arsenic and Antimony Azide Species

“…The identity of both compounds was confirmed by elemental analysis. The 1 H and 13 C NMR as well as the 31 …”

“…Materials and Apparatus . Activated NaN 3 , [AsCl 4 ][AsF 6 ], [Me 4 N][AsCl 4 ], As(N 3 ) 5 ·py, [SbCl 4 ][Sb 2 F 11 ], [Ph 4 P][SbCl 4 ], and [Et 4 N][SbCl 6 ] were prepared by literature methods. A solution of HN 3 in CH 2 Cl 2 was prepared by a modified literature method …”

Das Carbonylchlor(I)-Kation [ClCO]+

“…[9] Im Laufe von drei Tagen werden die Banden von [ClCO] immer schwächer. Aus der Suspension entsteht eine klare Flüssigkeit, und es bildet sich unter anderem [SbCl 4 ] (444, 392, 140, 125 cm À1 ), [17,18] was auf einen Cl/F-Austausch schlieûen läût. Im IR-Spektrum der überstehenden Gasphase lassen sich COFCl, COF 2 sowie auch etwas CF 4 und CO 2 nachweisen.…”