Synthesis and Reactivity of Triangular Heterometallic Complexes Containing Zn-Zn Bond

This work provides a facile access to a series of triangular [Zn₂M] (M = group 10 and 11 metals) clusters. Treatment of Zn-Zn-bonded compounds [LZn-ZnL] (L = CH₃C(2,6-Pr₂C₆H₃N)CHC(CH₃)(NCH₂CH₂PR₂); R = Ph, Pr) with zero-valent transition-metal reagents selectively afforded the corresponding triangular clusters [Zn₂M], where M = Ni(0), Pd(0), and Pt(0). Notably, the isoelectronic triangular clusters [Zn₂M]⁺, where M = Ag(I) and Cu(I), could also be obtained by reactions of [LZn-ZnL] with AgOTf and CuOTf, respectively. The [Zn₂Ag]⁺ complex containing elusive Zn-Ag bonds was investigated by density functional theory analysis, showing a 3c-2e bonding feature in the metallic ring. The electrochemical behaviors of [Zn₂M] complexes were examined and revealed the donation of electron density from the Zn-Zn σ-bond to the metal centers. Reaction of the [Zn₂Ni] complex with isocyanide gave heterometallic species by coordination of isocyanide to the nickel center, keeping the trimetallic ring core structure intact. In contrast, the Zn-Zn bond was rapidly cleaved upon treatment of the [Zn₂Ni] complex with dihydrogen or phenyl acetylene, generating the hydride- or acetylide-bridged heterotrimetallic complex.