A regioselective nitration of BN-substituted arene compounds has been successfully developed. The first examples of BN-nitroarenes have been synthesized and structurally characterized by X-ray diffraction analysis. Photophysical studies of these novel compounds reveal an effective π conjugation between the nitro group and 1,2-azaborine moiety in the solution phase. A plausible mechanism for this nitration reaction is proposed.

The acylation reaction of BN-arenes has been studied using BN-arene and acyl chloride in good to excellent yields, which led to the first synthesis of indanone BN-analogue. The BN-aromatic ketone products have been characterized by 1H NMR spectroscopy with their molecular structures unambiguously confirmed by X-ray crystallography. The annulation reaction of BN-arenes promoted by AgBF4 occurs in a completely regioselective manner and a mechanism for this transformation is proposed.

The synthesis and characterization of 1,2-azaborolyl (Ab)-ligated titanium(IV) half-metallocene complexes are presented, and their catalytic properties in ethylene polymerization have been evaluated. Mono-Ab TiCl3 complexes 3 and 4 can be conveniently converted to other half-metallocene derivatives (5–8) in moderate to good yields. The molecular structures of titanium complexes 3–8 have been determined by X-ray diffraction analysis. Upon activation with methylaluminoxanes (MAO), mono-Ab Ti half-metallocenes demonstrated high catalytic activity in ethylene polymerization (1.50 × 107 g of PE (mol of Ti)−1 h–1) at a low [MAO] (Al:Ti = 30) .

The preparation of a new class of triarylphosphine ligands consisting of the 4a,8a-azaboranapthalene-4-yl (ABN) group is disclosed. X-ray analysis and DFT calculations demonstrate a characteristic π-conjugation system of ABN-phosphine 3, which has been evaluated as a supporting ligand in Pd-catalysed Suzuki–Miyaura coupling reactions of aryl halides and phenyl boronic acid.

A concise and effective three-step synthesis of 4a,8a-azaboranaphthalene (ABN) has been developed in gram scale. Electrophilic aromatic substitution reactions of ABN provide excellent functional-group-tolerant cross-coupling partners in various Pd-catalyzed cross-coupling reactions (e.g., Sonogashira, Suzuki–Miyaura, or Heck reaction). Photophysical, electrochemical, and DFT calculations all suggest a narrowed HOMO–LUMO gap with extended π-conjugation characters in the cross-coupled molecules. The ABN moiety as a new fluorophore has a distinct and selective fluorescence response toward Zn(II) and Cd(II) ions, demonstrating great potential for the ABN structural motif in fluorescent chemosensors.