Polyfluorides and Neat Fluorine as Host Material in Matrix‐Isolation Experiments

Abstract

The use of neat fluorine in matrix isolation is reported, as well as the formation of polyfluoride monoanions under cryogenic conditions. Purification procedures and spectroscopic data of fluorine are described, and matrix shifts of selected molecules and impurities in solid fluorine are compared to those of common matrix gases (Ar, Kr, N2 , Ne). The reaction of neat fluorine and IR-laser ablated metal atoms to yield fluorides of chromium (CrF5 ), palladium (PdF2 ), gold (AuF5 ), and praseodymium (PrF4 ) has been investigated. The fluorides have been characterized in solid fluorine by IR spectroscopy at 5 K. Also the fluorination of Kr and the photo-dismutation of XeO4 have been studied by using IR spectroscopy in neat fluorine. Formation of the [F5 ](-) ion was obtained by IR-laser ablation of platinum in the presence of fluorine and proven in a Ne matrix at 5 K by two characteristic vibrational bands of [F5 ](-) at $\tilde \nu $=850.7 and 1805.0 cm(-1) and its photo-behavior.

Polyhalogen and Polyinterhalogen Anions from Fluorine to Iodine

“…[38] However,ac lear assignment of the observed 95 m/z peak in the flowing afterglow was not possible.IR-spectroscopic evidence for the free [F 5 ] À anion was first obtained in 2015 after co-deposition of laserablated transition metals with fluorine in solid neon under cryogenic conditions. [24,69] In addition to the absorption bands of the transition-metal fluorides,t he IR spectra showed ametal-independent band at 850 cm À1 ,which vanished during irradiation with red light and was assigned to the antisymmetric stretch of [F 5 ] À .T hese findings contradicted the calculations,w hich had predicted ah ockey stick structure for the anion with, at least, two FÀFstretching vibrations.The explanation of this contradiction is still the objective of ongoing high-level quantum-chemical investigations.T he [F 5 ] À yields obtained after co-deposition of laser-ablated platinum with fluorine were exceptionally high so that the resulting IR spectra showed an additional band at 1805 cm À1 , which behaved like the 850 cm À1 band during irradiation with red light and was assigned to the combination vibration of the symmetric and antisymmetric stretches of the pentafluoride species.F igure 9s hows the calculated V-shaped and hockeystick structures of pentafluoride.T able 5provides asummary of all experimental and calculated spectroscopic data for…”

“…Band position neon ("V-shape") [69] n s + n as 1805 n as 850 calculated ("hockey stick") [45] n(F 2 )8 05 (76) [a] n as (F 3 )5 28 (639) [a] [a] Harmonic vibrationalf requencies (CCSD(T)/aug-cc-pVTZ). [45] Calculated IR intensities in parentheses.…”

Polyhalogen‐ und Polyinterhalogen‐Anionen von Fluor bis Iod

“…Allerdings war keine exakte Zuordnung des Signals im Flowing Afterglow bei m / z =95 möglich. Hinweise auf ein freies [F 5 ] − ‐Anion aus IR‐spektroskopischen Untersuchungen gab es erstmals 2015 als Ergebnis der gemeinsamen Abscheidung von laserablatiertem Metall und Fluor unter Tieftemperaturbedingungen in festem Neon . Neben Absorptionsbanden der Übergangsmetallfluoride zeigten die IR‐Spektren eine metallunabhängige Bande bei 850 cm −1 , die bei Bestrahlung mit rotem Licht verschwand und der antisymmetrischen Streckschwingung von [F 5 ] − zugeordnet wurde.…”

“…Hinweise auf ein freies [F 5 ] À -Anion aus IR-spektroskopischen Untersuchungen gab es erstmals 2015 als Ergebnis der gemeinsamen Abscheidung von laserablatiertem Metall und Fluor unter Tieftemperaturbedingungen in festem Neon. [24,69] Neben Absorptionsbanden der Übergangsmetallfluoride zeigten die IR-Spektren eine metallunabhängige Bande bei 850 cm À1 ,die bei Bestrahlung mit rotem Licht verschwand und der antisymmetrischen Streckschwin- [a], [60] 388 (2) [c], [24] 478 [d], [63] n s (F 3 ) 165 (35) [c], [24] 173 [d], [63] d(F 3 ) 561 [b], [24] 550 [b], [60] 551 [b], [65] 547 [b], [65] 568(262) [c], [24] 588 [d], [63] n as (F 3 ) 923 [b], [65] 919 [b], [65] n s (F 3 ) + n as (F 3 ) RbF 3 460 [b], [60] 390 [e], [63] 481 [d], [63] n s (F 3 ) 188 [d], [63] d(F 3 ) 550 [b], [60] 569 [e], [63] 590 [d], [63] n as (F 3 ) [63] 488 [d], [63] n s (F 3 ) 210 [d], [63] d(F 3 ) 549 [b],…”

Synthesis and Characterization of [Br3][MF6] (M=Sb, Ir), as well as Quantum Chemical Study of [Br3]+ Structure, Chemical Bonding, and Relativistic Effects Compared with [XBr2]+ (X=Br, I, At, Ts) and [TsZ2]+ (Z=F, Cl, Br, I, At, Ts)

“…Heteropolyhalide anions F[ F 3 ] À , [14][15][16] [F 5 ] À [14,17] Cl [Cl 3 ] À , [18][19][20][21][22][23][24] [Cl 5 ] À , [19] [Cl 8 ] 2À [25,26] [ClF 2 ] À , [27][28][29] [ClF 4 ] À , [30][31][32] [ClF 6 ] À , [33] [ClBr 6 ] À , [34] [ClI 4 ] À , [34] [Cl(I 2 ) 4 ] À [35] Br [Br 3 ] À , [36,37] [Br 5 ] À , [36] [Br 7 ] À , [36] [Br 9 ] À , [36,[38][39][40][41] [Br 11 ] À , [42] [Br 6 ] 2À , [43] [Br 8 ] 2À , [37] [Br 10 ] 2À , [44] [Br 20 ] 2À , [45,46] [Br 24 ] 2À [47] [BrF 2 ] À , [48][49][50] [BrF 4 ] À , [51][52][53][54][55]…”