|Molar mass||29.81 g·mol−1|
|200.48 J K−1 mol−1|
Std enthalpy of
|115.90 kJ mol−1|
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Boron monofluoride or fluoroborylene is a chemical compound with formula BF, one atom of boron and one of fluorine. It was discovered as an unstable gas and only in 2009 found to be a stable ligand combining with transition metals, in the same way as carbon monoxide. It is a subhalide, containing fewer than the normal number of fluorine atoms, compared with boron trifluoride. BF is isoelectronic with carbon monoxide and dinitrogen and each molecule has 14 electrons.
BF is unusual in that the dipole moment is inverted with fluorine having a positive charge even though it is the more electronegative element. This is explained by the 2sp orbitals of boron being reoriented and having a higher electron density. Backbonding, or the transfer of π orbital electrons for the fluorine atom is not required to explain the polarization.
BF can react with itself to form polymers of boron containing fluorine with between 10 and 14 boron atoms. BF reacts with BF3 to form B2F4. BF and B2F4 further combine to form B3F5. B3F5 is unstable above −50 °C and forms B8F12. This substance is a yellow oil.
BF reacts with acetylenes to make the 1,4-diboracyclohexadiene ring system. BF can condense with 2-butyne forming 1,4-difluoro-2,3,5,6-tetramethyl-1,4-diboracyclohexadiene. Also, it reacts with acetylene to make 1,4-difluoro-1,4-diboracyclohexadiene. Propene reacts to make a mix of cyclic and non-cyclic molecules which may contain BF or BF2.
BF hardly reacts with C2F4 or SiF4. BF does react with arsine, carbon monoxide, phosphorus trifluoride, phosphine and phosphorus trichloride to make adducts like (BF2)3B•AsH3, (BF2)3B•CO, (BF2)3B•PF3, (BF2)3B•PH3 and (BF2)3B•PCl3.
Vidovic and Aldridge reacted NaRu(CO)2(C5H5) with (Et2O)·BF3. Note that the BF was formed in place rather than added on.
By reacting iron vapour with B2F4 and PF3 a substance with the formula (PF3)FeBF was produced. Hafnium, Thorium, Titanium and Zirconium can form a difluoride with a BF ligand at the low temperature of 6K. These come about by reacting the atomic metal with BF3.
BF is isoelectronic with carbon monoxide (CO) and so could form similar compounds to metal carbonyls. It is predicted to also bridge between two or three metal atoms (μ2 and μ3). Working with BF as a ligand is difficult due to its instability in the free state.
- Hildenbrand, Donald L.; Murad, Edmond (1965). "Dissociation Energy of Boron Monofluoride from Mass-Spectrometric Studies". The Journal of Chemical Physics 43 (4): 1400. doi:10.1063/1.1696932.
- Vidovic, Dragoslav; Aldridge, Simon (2011). "Coordination chemistry of group 13 monohalides". Chemical Science 2 (4): 601. doi:10.1039/C0SC00508H.
- Nesbet, R. K. (1964). "Electronic Structure of N2, CO, and BF". The Journal of Chemical Physics 40 (12): 3619. doi:10.1063/1.1725063.
- Cazzoli, G.; Cludi, L.; Degli Esposti, C.; Dore, L. (1989). "The millimeter and submillimeter-wave spectrum of boron monofluoride: Equilibrium structure". Journal of Molecular Spectroscopy 134 (1): 159–167. Bibcode:1989JMoSp.134..159C. doi:10.1016/0022-2852(89)90138-0. ISSN 0022-2852.
- Martinie, R. J.; Bultema, J. J.; van der Wal, M. N.; Burkhart, B. J.; van der Griend, D. A.; de Kock, R. L. (2011). "Bond Order and Chemical Properties of BF, CO, and N2". Journal of Chemical Education 88 (8): 1094–1097. doi:10.1021/ed100758t.
- Fantuzzi, Felipe; Cardozo, Thiago Messias; Nascimento, Marco Antonio Chaer (28 May 2015). "Nature of the Chemical Bond and Origin of the Inverted Dipole Moment in Boron Fluoride: A Generalized Valence Bond Approach". The Journal of Physical Chemistry A 119 (21): 5335–5343. doi:10.1021/jp510085r.
- Timms, P. L. (1972). "Low Temperature Condensation". Advances in Inorganic Chemistry and Radiochemistry. p. 143. ISBN 0-12-023614-1.
- Eyring, Leroy (1967). Advances in High Temperature Chemistry volume 1. Academic Press. p. 70.
- Xu, L.; Li, Q.; Xie, Y.; King , R. B.; Schaefer, H. F. (2010). "Prospects for Making Organometallic Compounds with BF Ligands: Fluoroborylene Iron Carbonyls". Inorganic Chemistry 49 (3): 1046–1055. doi:10.1021/ic901964f. PMID 20041690.
- Xu, L.; Li, Q.-S.; Xie, Y.; King, R. B.; Schaefer, H. F. III (2010). "Binuclear fluoroborylene manganese carbonyls". Inorganica Chimica Acta 363 (13): 3538–3549. doi:10.1016/j.ica.2010.07.013.
- Xu, Liancai; Li, Qian-shu; Xie, Yaoming; King, R. Bruce; Schaefer, Henry F. (15 March 2010). "Major Difference between the Isoelectronic Fluoroborylene and Carbonyl Ligands: Triply Bridging Fluoroborylene Ligands in Fe3(BF)3(CO)9 Isoelectronic with Fe3(CO)12". Inorganic Chemistry 49 (6): 2996–3001. doi:10.1021/ic902511m.
- Xu, Liancai; Li, Qian-shu; King, R. Bruce (May 2012). "Fluoroborylene ligands in binuclear ruthenium carbonyls: Comparison with their iron analogues". Polyhedron 38 (1): 44–49. doi:10.1016/j.poly.2012.02.003.