PbF[Br₂F₇], a Fluoridobromate(III) of a p‐Block Metal

Abstract

The compound PbF[Br 2 F 7 ] represents the first fluoridobromate(III) of a p-block element. It was synthesized in form of needle-shaped crystals among its colorless powder from the direct reaction of PbF 2 with BrF 3 . Powder X-ray diffraction, IR and Raman spectroscopy show that it was obtained in almost pure form with Pb 3 F 8 and Pb 2 F 6 as by-products. The single crystal structure was determined by X-ray diffraction. PbF[Br 2 F 7 ] crystallizes in space group P2 1 /c (No. 14) with a = 4.3698(3), b = 13.3767 (7), c = 12.0836(8) Å, = 97.509(5)°, V = 700.27(8) Å 3 , [a]

Preparation of Two Quantum‐Chemically Predicted, Isomeric [Br4F13]– Anions in the Solid State

“…[ 1,20 ] The bi‐ and trinuclear anions were synthesized by Lewis acid‐base reactions of [BrF 4 ] – anions with BrF 3 and have only recently been identified and their structures elucidated. The binuclear heptafluoridodibromate(III) anion [F 3 Br–(µ‐F)–BrF 3 ] – is known for the compounds A [Br 2 F 7 ] [ 21 ] ( A = Rb, [ 22 ] Cs [ 15,23 ] ), PbF[Br 2 F 7 ] [ 24 ] and the trinuclear decafluoridotribromate(III) anion [(µ 3 ‐F)(BrF 3 ) 3 ] – so far only for the compounds A [Br 3 F 10 ] ( A = Rb, Cs). [ 21,22 ] The structural formulas of the currently known anionic species are shown in Scheme 1, stereochemical aspects are not considered for simplicity.…”

Soluble Fluoridobromates as Well‐Behaved Strong Fluorination Reagents

“…The tetramethylammonium salt was obtained by a metathesis reaction from Cs[BrF 4 ] and [NMe 4 ]F. [12] If an excess of BrF 3 is used to dissolve RbCl, CsCl, CsF or PbF 2 larger anions of the type [F(BrF 3 ) n ]with n = 2 or 3 can be isolated. The [Br 2 F 7 ]with a bridging μ 2 -F atom is known as the Cs + , [15,16] Rb + [15,16] and [PbF] + [17] salt. The [Br 3 F 10 ]complex with a bridging μ 3 -F atom exists as the Rb + and Cs + salt.…”

Synthesis and Characterization of the Tetrafluoridochlorates(III) A[ClF4] (A = K, Rb, Cs)

“…More complex anions with higher M F 3 content, such as [ M 2 F 7 ] – and [ M 3 F 10 ] – , have been reported and are so far limited to the BrF 3 and AuF 3 systems . The [ M 2 F 7 ] – anions show a µ 2 ‐bridging fluorine atom and have been obtained in the compounds A [Br 2 F 7 ] ( A = Rb, Cs, PbF) and Cs[Au 2 F 7 ] . Thus far, the [Br 3 F 10 ] – anion has the highest M F 3 content, exhibiting a central µ 3 ‐bridging F atom, and was obtained as the Rb and Cs salts .…”