Reactivity of Cyclic (Alkyl)(amino)germylene towards Copper(I) and Gold(I) Complexes

Abstract

The reactions of cyclic (alkyl)(amino)germylenes (CAAGe) with copper(I) and gold(I) complexes were investigated. CAAGe (1) reacts with CuBr(SMe2) leading to a tetrameric germylene complex [CAAGeCuBr]4 (2), whereas CAAGe (3) undergoes Au−Cl bond insertion with LAuCl (L=phosphine or N‐heterocyclic carbene) to afford germanium gold(I) complexes (5 and 6). Chlorine abstraction of 6 gives the cationic germylene gold(I) complex 7.

Recent advances in the chemistry of isolable carbene analogues with group 13–15 elements

“…Notably, germylene 82a also demonstrates versatility in forming Ge–Au( i ) complexes 82a-P5–P6 through Au–Cl bond insertion. 269 In contrast, 82b undergoes a reaction with CuBr(SMe 2 ) to yield tetrameric complex 82b-P . Furthermore, within a borane B(C 6 F 5 ) 3 -catalyzed environment, germylene 82b can be transformed into seven other germylenes 82c-i through a Si–C/Si–H cross-metathesis reaction with corresponding hydrosilanes.…”

Crystalline Cyclic (Alkyl)(Amino)Stannylene via Transient Stannyne

“…[23] These diverse electronic properties significantly enhance their versatility in key applications including coordination chemistry and small molecule activation. Following the progressive advancements in CAAC chemistry, the groups led by Kinjo, Iwamoto, Yamashita and Cowley made important contributions by isolating CAAC analogous [9] incorporating main group elements such as boron, [26] aluminum, [27][28][29] silicon, [30][31][32][33][34][35][36][37][38][39] germanium, [40][41][42][43] phosphorus, [44,45] and arsenic. [44] For heavier group 14 analogues, cyclic (alkyl)(amino)silylenes (CAASis) and cyclic (alkyl)(amino)germylenes (CAAGes) have emerged as potent ligands and synthons for crafting novel silicon and germanium species (Figure 1b).…”

“…[44] For heavier group 14 analogues, cyclic (alkyl)(amino)silylenes (CAASis) and cyclic (alkyl)(amino)germylenes (CAAGes) have emerged as potent ligands and synthons for crafting novel silicon and germanium species (Figure 1b). [30][31][32][33][34][35][36][37][38][39][40][41][42][43] Notwithstanding the extensive exploration of tin analogues of NHCs, [7-9, 12, 13] and the identification of a few acyclic (alkyl)(amino)stannylenes (aCAASn) such as A by Jones and Frenking, [46] cyclic (alkyl)(amino)stannylenes (CAASn) still represent a frontier yet to be charted.…”