Aromatic 1,2-Azaborinin-1-yls as Electron-Withdrawing Anionic Nitrogen Ligands for Main Group Elements

The 2-aryl-3,4,5,6-tetraphenyl-1,2-azaborinines 1-EMe₃ and 2-EMe₃ (E=Si, Sn; aryl=Ph (1), Mes (=2,4,6-trimethylphenyl, 2)) were synthesized by ring-expansion of borole precursors with N₃ EMe₃ -derived nitrenes. Desilylative hydrolysis of 1- and 2-SiMe₃ yielded the corresponding N-protonated azaborinines, which were deprotonated with nBuLi or MN(SiMe₃ )₂ (M=Na, K) to the corresponding group 1 salts, 1-M and 2-M. While the lithium salts crystallized as monomeric Lewis base adducts, the potassium salts formed coordination polymers or oligomers via intramolecular K⋅⋅⋅aryl π interactions. The reaction of 1-M or 2-M with CO₂ yielded N-carboxylate salts, which were derivatized by salt metathesis to methyl and silyl esters. Salt metathesis of 1-M or 2-M with methyl triflate, [Cp*BeCl] (Cp*=C₅ Me₅ ), BBr₂ Ar (Ar=Ph, Mes, 2-thienyl), ECl₃ (E=B, Al, Ga) and PX₃ (X=Cl, Br) afforded the respective group 2, 13 and 15 1,2-azaborinin-2-yl complexes. Salt metathesis of 1-K with BBr₃ resulted not only in N-borylation but also Ph-Br exchange between the endocyclic and exocyclic boron atoms. Solution ¹¹ B NMR data suggest that the 1,2-azaborinin-2-yl ligand is similarly electron-withdrawing to a bromide. In the solid state the endocyclic bond length alternation and the twisting of the C₄ BN ring increase with the sterics of the substituents at the boron and nitrogen atoms, respectively. Regression analyses revealed that the downfield shift of the endocyclic ¹¹ B NMR resonances is linearly correlated to both the degree of twisting of the C₄ BN ring and the tilt angle of the N-substituent. Calculations indicate that the 1,2-azaborinin-1-yl ligand has no sizeable π-donor ability and that the aromaticity of the ring can be subtly tuned by the electronics of the N-substituent.