Bis(1-Methyl-ortho-Carboranyl)Borane.

The Lewis superacid, bis(1-methyl-ortho-carboranyl)borane, is rapidly accessed in two steps. It is a very effective hydroboration reagent capable of B-H addition to alkenes, alkynes, and cyclopropanes. To date, this is the first identified Lewis superacidic secondary borane and most reactive neutral hydroboration reagent.

Triple-Decker Iron and Cobalt Complexes Featuring a Bridging 1,2-Diboratabenzene Ligand.

Neutral triple-decker iron and cobalt complexes with a bridging 1,2-diboratabenzene ligand were accessed by reactions of a dilithium 1,2-diboratabenzene reagent with [Cp*FeCl]2 and [Cp*CoCl]2, respectively. While 1,2-diboratabenzene metal complexes are known, these represent the first examples of the ligand bridging two metals.

Probing borafluorene B-C bond insertion with gold acetylide and azide.

The reaction of Ph3PAuN3 with 9-Ph-9-borafluorene resulted in complexation of the azide to boron while a gold acetylide reacted with 9-Ph-9-borafluorene to insert the acetylide carbon to access a six-membered boracycle with an exocyclic double bond.

Tris(ortho-carboranyl)borane: An Isolable, Halogen-Free, Lewis Superacid.

The synthesis of tris(ortho-carboranyl)borane (BoCb3 ), a single site neutral Lewis superacid, in one pot from commercially available materials is achieved. The high fluoride ion affinity (FIA) confirms its classification as a Lewis superacid and the Gutmann-Beckett method as well as adducts with Lewis bases indicate stronger Lewis acidity over the widely used fluorinated aryl boranes. The electron withdrawing effect of ortho-carborane and lack of pi-delocalization of the LUMO rationalize the unusually high Lewis acidity. Catalytic studies indicate that BoCb3 is a superior catalyst for promoting C-F bond functionalization reactions than tris(pentafluorophenyl)borane [B(C6 F5 )3 ].

Accessing Boron-Doped Pentaphene Analogues from 12-Boradibenzofluorene.

Borole-doped polycyclic aromatic hydrocarbons (PAHs) have garnered attention in recent years due to their attractive photophysical properties and potential utility in electronic devices. In this work, a borole-doped PAH, 12-boradibenzofluorene, is synthesized and formal intermolecular nitrene and oxygen atom insertion reactions were employed to access 1,2-azaborine- and 1,2-oxaborine-containing analogues of the carbonaceous PAH pentaphene. Iodosobenzene is established as a versatile reagent for oxygen atom insertion reactions into a variety of borole species to access 1,2-oxaborine systems.

Antimony diiminopyridine complexes.

The stoichiometric reactions of antimony trichloride, trimethylsilyl trifluoromethanesulfonate, and diiminopyridine ligands lead to the formation of N,N',N''-chelated SbCl2 cationic complexes. Methyl and phenyl substituents on the imine carbons of the ligand yielded structures with a lone pair on antimony and the hydrogen substituted variant was notably different as it forms a Menshutkin complex with meta-xylene in the solid-state.

9-Borafluorenes: Synthesis, Properties, and Reactivity.

This review covers all aspects of 9-borafluorene chemistry, from the first attempted synthesis in 1960 to the present. This class of molecules consists of a tricyclic system featuring a central antiaromatic BC4 ring with two fused arene groups. The synthetic routes to all 9-borafluorenes and their adducts are presented. The Lewis acidity and photophysical properties outlined demonstrate potential utility as sensors and in electronic materials. The reactivity of borafluorenes reveals their prospects as reagents for the synthesis of other boron-containing molecules. The appealing traits of 9-borafluorenes have stimulated investigations into analogues that bear different aromatic groups fused to the central BC4 ring. Finally, we offer our views on the challenges and future of borafluorene chemistry.