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)(2)(mu,eta(1:1)-As-2)] (n=1 (1), 4 (2)), [(CAAC-2)(3)(mu(3),eta(1:1:1)-As-4)] (3) and [(CAAC-3)(4)(mu(4),eta(1:1:1:1)- As-8)] (6) were isolated due to the differing steric properties of CAAC-1-4. The products contain As-2, As-4 or As-8 units and represent the first examples of CAACs-substituted products of yellow arsenic. The reactivity of As-4 was compared with the reactivities of P-4 and the interpnictogen compound AsP3, which led to a series of phosphorus-containing derivatives such as ([(CAAC-3)(3)(mu(3),eta(1:1:1)-P-4)] (4) and [(CAAC-3)(4)(mu(4),eta(1:1:1:1)-P-8)] (7)) and [(CAAC-3)(3)(mu(3),eta(1:1:1)-AsP3)] (5). The products were characterized by spectroscopic and crystallographic methods and DFT computations were performed to clarify their formation pathway.

Automated summary

Different cyclic (alkyl)(amino)carbenes (CAACs) reacted with yellow arsenic to yield various products, including As-2, As-4, and As-8 units. These products represent the first examples of CAACs-substituted products of yellow arsenic. Spectroscopic and crystallographic methods were used to characterize the products and DFT computations were performed to explain their formation pathway.