Reactivity of Yellow Arsenic towards Cyclic (Alkyl)(Amino) Carbenes (CAACs).

Different cyclic (alkyl)(amino)carbenes (CAACs) were reacted with yellow arsenic. Several products [(CAAC-n) (μ,η -As )] (n=1 (1), 4 (2)), [(CAAC-2) (μ ,η -As )] (3) and [(CAAC-3) (μ ,η - As )] (6) were isolated due to the differing steric properties of CAAC-1-4. The products contain As , As or As units and represent the first examples of CAACs-substituted products of yellow arsenic. The reactivity of As was compared with the reactivities of P and the interpnictogen compound AsP , which led to a series of phosphorus-containing derivatives such as ([(CAAC-3) (μ ,η -P )] (4) and [(CAAC-3) (μ ,η -P )] (7)) and [(CAAC-3) (μ ,η -AsP )] (5). The products were characterized by spectroscopic and crystallographic methods and DFT computations were performed to clarify their formation pathway.