Bromine Monofluoride

Abstract

BrF can be prepared by reaction of Br 2 and F 2 in various solvents below -100°C. In solution it is identified by 19 F NMR and Raman spectroscopy. From CH 3 Cl solution a single crystal structure determination of a BrF/CH 3 Cl adduct was obtained. The preparation from BrF 3 and Br 2 at 600°C also delivers BrF in small amounts. The crystal structure of BrCl comes in an ordered and a disordered variety. 2106The ordered structure is made of Br-Cl···Br-Cl chains. Computations suggest that neat BrF crystallizes in a dipol-dipole type polymeric structure rather than a halogen bonded one as in ClF. A possible intermediate along the decomposition pathway into BrF 3 and Br 2 is Br-BrF 2 .

High-pressure stabilization of open–shell bromine fluorides

“…Our calculations also successfully reproduced the thermodynamic stability of BrF 3 and BrF 5 at ambient pressure, as well as the lack of stability of BrF with respect to decomposition into bromine and BrF 3 . 58 It is noteworthy pointing out that a recent computation study proposed various high-pressure phases of bromine monofluoride, but without estimating its stability with respect to decomposition into other fluorides. 59 Our results indicate the same transition sequence as given in that study, but with slightly different transition pressures ().…”

Polycentric binding in complexes of trimethylamine-N-oxide with dihalogens

“… a Ccomputations were made in B3LYP-D/DZV, 65 PBE0/def2-TZVPPD, 66 CCSD(T) aug-cc-pVTZ/, 67 MP2/aug-cc-pVTZ, 70 CCSD(T)/aug-cc-pV(5+d)Z and CCSD(T)/aug-cc-pRV5Z, 78 CCSD(T)/aug-cc-pVTZ, 79 B3LYP/LANL2DZ, 80 and MP2/6-311++G(2D) 81 (for dimer). For a large set of precise computations for dihalogens, see ref.…”

Halogens

“…The first X-ray crystal structure of BrF has been obtained as a CHCl 3 adduct with an essentially linear array of ClÁ Á ÁBr-F (179.01). 28 The Br-F bond length (182.2(2) pm) is marginally longer than in the gas phase concomitant with a lengthening of C-Cl in CHCl 3 . In the same study the crystal structure of neat Br-Cl was also determined.…”

“…Highlights of the 2012 literature concerning the halogens include the first direct evidence of naturally occurring elemental fluorine, 1 the first X-ray crystal structure of BrF, 28 as well as the structural characterisation of several new hypervalent iodine compounds. [49][50][51][52][53][54]…”