Despite steady progress in catalytic methods for the borylation of hydrocarbons, methane has not yet been subject to this transformation. Here we report the iridium-catalyzed borylation of methane using bis(pinacolborane) in cyclohexane solvent. Initially, trace amounts of borylated products were detected with phenanthroline-coordinated Ir complexes. A combination of experimental high-pressure and high-throughput screening, and computational mechanism discovery techniques helped to rationalize the foundation of the catalysis and identify improved phosphine-coordinated catalytic complexes. Optimized conditions of 150°C and 3500-kilopascal pressure led to yields as high as ∼52%, turnover numbers of 100, and improved chemoselectivity for monoborylated versus diborylated methane.

The treatment of [{Ti(η(5)-C5Me5)}4(μ3-N)4] with NH3BH3 leads to the paramagnetic imidonitrido complex [{Ti(η(5)-C5Me5)}4(μ3-N)3(μ3-NH)], which can also be obtained by stepwise proton and electron transfer with HOTf and [K(C5Me5)].

Simple exposure of a hexane solution of [TiCp*Me ] (Cp*=η -C Me ) to an atmosphere of commercially available and inexpensive forming gas (H /N mixture, 13.5-16.5 % of H ) at room temperature leads to the methylidene-methylidyne-nitrido cube-type complex [(TiCp*) (μ -CH)(μ -CH )(μ -N) ] via dinitrogen cleavage. This paramagnetic compound reacts with [D ]chloroform to give the titanium(IV) methylidyne-nitrido species [(TiCp*) (μ -CH) (μ -N) ], whereas its one-electron oxidation with AgOTf or [Fe(η -C H ) ](OTf) (OTf=O SCF ) yields the diamagnetic ionic derivative [(TiCp*) (μ -CH)(μ -CH )(μ -N) ](OTf). The μ -nitrido ligands of the methylidyne-nitrido cubane complex can be protonated with [LutH](OTf) (Lut=2,6-lutidine) or hydrogenated with NH ⋅BH to afford μ -NH imido moieties.

Alkylation of [{Ti(η(5)-C(5)Me(5))(μ-NH)}(3)(μ(3)-N)] with MeOTf occurs at the imido ligands to produce the methylamido derivative [Ti(3)(η(5)-C(5)Me(5))(3)(μ(3)-N)(μ-NH)(2)(μ-NHMe)(OTf)] which readily rearranges to form the methylimido complex [Ti(3)(η(5)-C(5)Me(5))(3)(μ(3)-N)(μ-NH)(μ-NH(2))(μ-NMe)(OTf)].

Several trinuclear titanium complexes bearing amido μ-NHR, imido μ-NR, and nitrido μn-N ligands have been prepared by reaction of [{Ti(η(5)-C5Me5)(μ-NH)}3(μ3-N)] (1) with 1 equiv of electrophilic reagents ROTf (R = H, Me, SiMe3; OTf = OSO2CF3). Treatment of 1 with triflic acid or methyl triflate in toluene at room temperature affords the precipitation of compounds [Ti3(η(5)-C5Me5)3(μ3-N)(μ-NH)2(μ-NH2)(OTf)] (2) or [Ti3(η(5)-C5Me5)3(μ3-N)(μ-NH)(μ-NH2)(μ-NMe)(OTf)] (3). Complexes 2 and 3 exhibit a fluxional behavior in solution consisting of proton exchange between μ-NH2 and μ-NH groups, assisted by the triflato ligand, as could be inferred from a dynamic NMR spectroscopy study. Monitoring by NMR spectroscopy the reaction course of 1 with MeOTf allows the characterization of the methylamido intermediate [Ti3(η(5)-C5Me5)3(μ3-N)(μ-NH)2(μ-NHMe)(OTf)] (4), which readily rearranges to give 3 by a proton migration from the NHMe amido group to the NH imido ligands. The treatment of 1 with 1 equiv of Me3SiOTf produces the stable ionic complex [Ti3(η(5)-C5Me5)3(μ3-N)(μ-NH)2(μ-NHSiMe3)][OTf] (5) with a disposition of the nitrogen ligands similar to that of 4. Complex 5 reacts with 1 equiv of [K{N(SiMe3)2}] at room temperature to give [Ti3(η(5)-C5Me5)3(μ3-N)(μ-N)(μ-NH)(μ-NHSiMe3)] (6), which at 85 °C rearranges to the trimethylsilylimido derivative [Ti3(η(5)-C5Me5)3(μ3-N)(μ-NH)2(μ-NSiMe3)] (7). Treatment of 7 with [K{N(SiMe3)2}] affords the potassium derivative [K{(μ3-N)(μ3-NH)(μ3-NSiMe3)Ti3(η(5)-C5Me5)3(μ3-N)}] (8), which upon addition of 18-crown-6 leads to the ion pair [K(18-crown-6)][Ti3(η(5)-C5Me5)3(μ3-N)(μ-N)(μ-NH)(μ-NSiMe3)] (9). The X-ray crystal structures of 2, 5, 6, and 8 have been determined.