Binding, Release and Functionalization of Intact Pnictogen Tetrahedra Coordinated to Dicopper Complexes.

Abstract

The bridging MeCN ligand in the dicopper(I) complexes [(DPFN)Cu2(μ,η1 : η1‐MeCN)][X]2 (X=weakly coordinating anion, NTf2 (1 a), FAl[OC6F10(C6F5)]3 (1 b), Al[OC(CF3)3]4 (1 c)) was replaced by white phosphorus (P4) or yellow arsenic (As4) to yield [(DPFN)Cu2(μ,η2 : η2‐E4)][X]2 (E=P (2 a–c), As (3 a–c)). The molecular structures in the solid state reveal novel coordination modes for E4 tetrahedra bonded to coinage metal ions. Experimental data and quantum chemical computations provide information concerning perturbations to the bonding in coordinated E4 tetrahedra. Reactions with N‐heterocyclic carbenes (NHCs) led to replacement of the E4 tetrahedra with release of P4 or As4 and formation of [(DPFN)Cu2(μ,η1 : η1‐MeNHC)][X]2 (4 a,b) or to an opening of one E−E bond leading to an unusual E4 butterfly structural motif in [(DPFN)Cu2(μ,η1 : η1‐E4 DippNHC)][X]2 (E=P (5 a,b), E=As (6)). With a cyclic alkyl amino carbene (EtCAAC), cleavage of two As−As bonds was observed to give two isomers of [(DPFN)Cu2(μ,η2 : η2‐As4 EtCAAC)][X]2 (7 a,b) with an unusual As4‐triangle+1 unit.