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Cyclotriarsanes are rare and limited synthetic approaches have hampered reactivity studies on these systems. Described in here is a scalable synthetic protocol towards (AsAr)<sub>3</sub> (Ar = Dip, 2,6-<sup>i</sup>Pr<sub>2</sub>-C<sub>6</sub>H<sub>3</sub>; Tip, 2,4,6-<sup>i</sup>Pr<sub>3</sub>-C<sub>6</sub>H<sub>2</sub>), which allowed to study their reactivity towards [Cp<sub>2</sub>Ti(C<sub>2</sub>(SiMe<sub>3</sub>)<sub>2</sub>], affording titanocene diarsene complexes and towards N-heterocyclic carbenes (NHCs) to give straightforward access to a variety of NHC-arsinidene adducts. The electronic structure of the titanium diarsene complxes has been studied and they are best described as Ti(IV) species with a doubly reduced As<sub>2</sub>Ar<sub>2</sub> ligand. These findings will make (AsAr)<sub>3</sub> valuable precursors in the synthetic inorganic and organic chemistry.


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