Reactivity of Yellow Arsenic towards Cyclic (Alkyl)(Amino) Carbenes (CAACs)
Maria Haimerl, Christoph Schwarzmaier, Christoph Riesinger, Alexey Y. Timoshkin, Mohand Melaïmi, Guy Bertrand, Manfred Scheer
Abstract
Abstract Different cyclic (alkyl)(amino)carbenes (CAACs) were reacted with yellow arsenic. Several products [(CAAC‐n) 2 (μ,η 1:1 ‐As 2 )] (n=1 ( 1 ), 4 ( 2 )), [(CAAC‐2) 3 (μ 3 ,η 1:1:1 ‐As 4 )] ( 3 ) and [(CAAC‐3) 4 (μ 4 ,η 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 AsP 3 , which led to a series of phosphorus‐containing derivatives such as ([(CAAC‐3) 3 (μ 3 ,η 1:1:1 ‐P 4 )] ( 4 ) and [(CAAC‐3) 4 (μ 4 ,η 1:1:1:1 ‐P 8 )] ( 7 )) and [(CAAC‐3) 3 (μ 3 ,η 1:1:1 ‐AsP 3 )] ( 5 ). The products were characterized by spectroscopic and crystallographic methods and DFT computations were performed to clarify their formation pathway.