Microwave Spectrum and Molecular Structure of Bromine Trifluoride

Abstract

Articles you may be interested inMicrowave spectrum and molecular structure of PNO

RbBrF4 Revisited

“…The experimentally determined Br-F distance in the title compound is 1.932(8) Å, which is very close to the values observed for KBrF 4 with 1.89(1) Å, [15] for CsBrF 4 with 1.94(4) to 1.97(4) Å, [12] for CsBr 2 F 7 with 1.7686(11) to 2.1431(12) Å, [12] for Ba(BrF 4 ) 2 with 1.801(4) to 1.935(2) Å, [13] and also to the bond lengths observed for BrF 3 molecules in the gas phase with 1.721 to 1.810 Å (no s.u. given), [22,23] and the BrF 3 molecules in their crystal structure with 1.71(1) to 1.888(9) Å, [24] as well as to the theoretically predicted Br-F distance in the isolated BrF 4 -anion (1.8994 Å). [25] If we carry out the refinement using the previous model of the crystal structure on our powder pattern (with the Rb atom on the 4c position) the Rietveld refinement produces very bad agreement factors: Rp = 0.4527, wRp = 0.5848, R(obs) = 0.6004, wR 2 (obs) = 0.5580, R(all) = 0.6522, wR 2 (all) = 0.5669.…”

Angles between orthogonal spd bond orbitals with maximum strength

“…This is, in fact, the structure of BrF3. Its microwave spectrum (12) (14), is that the orbitals for unshared pairs occupy a larger solid angle than bond orbitals. This rule is a consequence of the increase in stability of electron pairs with increased amount of s character and of bonds with increased amount of p character or d character.…”

Selective Reactions of Bromine Trifluoride in Organic Chemistry

“…Boguslavskaya treated 1,4-dihalobutanes 23 with BrF 3 in the presence of HF and SnCl 4 and obtained mainly two products: 1-halo-4-fluorobutanes 24 and the rearranged 1-halo-3-fluorobutanes 25 in various ratios ranging from 97:3 to 34:66 and in overall yields from 45% to 80%. [20] Similar results were obtained with fluorine-containing polyhalopropanes such as 1,3-dichloro-2-fluoropropane (26) converted to 2,2-difluorochloropropane (27) that resisted further reaction, and to 1-chloro-2,3-difluoropropane (28), which could undergo a further substitution to give 1,2,3-trifluoropropane (29).…”

“…[2] This method proved eventually to be the method of choice for the preparation of this compound as evident from quite a few similar reports that have appeared on the subject with minor changes for almost a century. [3] Spectroscopic studies using microwave [4] and X-ray [5] analyses have emerged as well, suggesting that the elements of this molecule are arranged in a "T" shape [6] and it exhibits electrical conductivity due to the existence of an ionic equilibrium between BrF 3 and the pair of ions BrF 4 À and BrF 2 + . [7] At that period organic chemists also began experimenting with this reagent, although hesitatingly, and reacted it with "small" amounts of hexafluorobenzene.…”