Borylene

As discussed above, free borylenes have yet to be isolated, but they have been the subject of a number of computational studies and have investigated spectroscopically and experimentally. B-R (R=H, F, Cl, Br, I, NH2, C2H, Ph) have been observed via microwave or IR spectroscopy at low temperature via elaborate procedures. When generated as reactive intermediates, borylenes have been shown to activate strong C-C single bonds, yielding products analogous to an organometallic oxidative addition reaction. Most commonly, these are generated via reduction of an organoborane dichloride, but photolysis of other boranes can also afford short-lived borylene species. As might be expected, calculations have demonstrated that the HOMO is composed of the nonbonding electrons on boron (nσ-type, sp character). The LUMO and LUMO+1 are empty, orthogonal pπ-type orbitals and are degenerate in energy except in the case where R breaks the symmetry of the molecule, thus lifting the degeneracy. Unlike carbenes, which can exist in either singlet or triplet ground states, calculations have indicated that all yet-studied borylenes have a singlet ground spin state. The smallest singlet-triplet gap was calculated to be 8.2 kcal/mol for Me3Si-B. Aminoborylene (H2NB) is a slight exception to the above paradigm, as the nitrogen lone pair donates into an unoccupied boron p orbital. Thus, there is formally a double bond between boron and nitrogen; the π* combination of this interaction serves as the LUMO+1. ==Mono-Lewis base-stabilized borylenes==

The first example of a borylene stabilized by a single Lewis base was reported in 2007 and exists as a dimer—a diborene. An (NHC)BBr3 adduct was reduced to generate a probable (NHC)B-H intermediate that subsequently dimerized to form the diborene. A similar species with a boron–boron single bond was also observed. The diborene has an incredibly short boron–boron bond length of 1.560(18) Å, further supporting the assignment of a double bond. DFT and NBO calculations were performed on a model system (with Dipp moieties replaced by H). Although some differences between the calculated and crystal structures were evident, they could primarily be ascribed to distortions from planarity caused by the bulky Dipp groups. The HOMO was calculated to be a B-B π-bonding orbital and the HOMO-1 is of mixed B-H and B-B σ-bonding character. NBO calculations supported the above assessments, as populations for the B-B σ- and π-bonding orbitals were calculated to be 1.943 and 1.382 respectively. The (NHC)borane adduct was prepared then reduced with Co(Cp*)2. One equivalent of reductant yielded an aminoboryl radical and a second reduction event lead to the desired (CAAC)borylene. The resulting dianion was subsequently oxidized to a neutral compound, and reduced using water. ==Bis-Lewis base-stabilized borylenes==

Taking inspiration from Robinson's above diborene synthesis, Reduction of (CAAC)BBr3 with KC8 in the presence of excess CAAC afforded the bis(CAAC)BH. A labeling study indicated that the H-atom was abstracted from an aryl group associated with the CAAC. Reduction of (CAAC)BBr3 yields the same terminal borylene even in the absence of additional Lewis base via a mechanism that remains poorly understood. Several other routes have also been proposed. A more novel one employs methyl triflate to abstract a hydride from (CAAC)BH3. Treatment with a Lewis base, followed by triflic acid and KC8 afford the desired (CAAC)(Lewis base)BH. Although the reported case uses only specific Lewis bases, the approach is argued to be highly generalizable. File:BisCAACborylene HOMO.png|left|thumb|Bis(CAAC)BH HOMO. ==Borylene-transition metal complexes==

The first transition metal complex reported by Braunschweig et al. featured a borylene ligand bridging between two manganese centers: [ μ-BX{η5-C5H4R}Mn(CO)2}2] (R=H, Me; X=NMe2). The first terminal borylene complex [(CO)5MBN(SiMe3)2] was prepared by the same group several years later. Two previous structures – [(CO)4Fe(BNMe2)] and [(CO)4Fe{BN(SiMe3)2}] – had been proposed by other groups but disqualified due to inconsistent 11B-NMR data. A number of diborylene complexes have also been described. The first of these, [(η5-C5Me5)Ir{BN(SiMe3)2}2], was prepared by the photochemical reaction of [(η5-C5Me5)Ir(CO)2] with [(OC)5Cr{BN(SiMe3)2}]. One unusual reaction exhibited by these complexes is coupling of borylene and carbon monoxide ligands. Catenation of an iron borylene complex has generate an iron complex of a tetraboron (B4) chain. Orbitally, the interactions between transition metals and borylenes tend to be similar to the above Lewis acids and borylenes. A number of computational studies have been performed on these systems. A sample paper from 2000 employed NBO to analyze a series of related complexes. Taking [(CO)4Fe{BN(SiH3)2}] as an example, it was calculated that—as expected—the boron moiety is relatively electron-poor (+0.59 charge). The Fe-B π-bonding orbitals were found to have populations of 0.39 and 0.48 whereas the σ-bonding had 0.61. Thus, the Wiberg bond index of the Fe-B bond was a relatively strong 0.65 (compare: Fe-CO was 0.62 in the same complex. The analogous tungsten complex had a bond index value of 0.82. Overall, the paper concludes that transition metal-borylene bonds are very strong. However, the bonding has strong ionic contributions. Orbital attractions are primarily σ- accompanied by weaker π-interactions. Unlike corresponding metal-carbyne complexes, the bond order in all studied cases was less than 1. ==References==