Cluster dynamics of heterometallic trinuclear clusters during ligand substitution, redox chemistry, and group transfer processes

Stepwise metalation of the hexadentate ligand tbs LH 6 ( tbs LH 6 = 1,3,5-C 6 H 9 (NHC 6 H 4 - o -NHSiMe 2 t Bu) 3 ) affords bimetallic trinuclear clusters ( tbs L)Fe 2 Zn(thf) and ( tbs L)Fe 2 Zn(py). Reactivity studies were pursued to understand metal atom lability as the clusters undergo ligand substitution, redox chemistry, and group transfer processes. Chloride addition to ( tbs L)Fe 2 Zn(thf) resulted in a mixture of species including both all-zinc and all-iron products. Addition of ArN 3 (Ar = Ph, 3,5-(CF 3 ) 2 C 6 H 3 ) to ( tbs L)Fe 2 Zn(py) yielded a mixture of two trinuclear products: ( tbs L)Fe 3 (μ 3 -NAr) and ( tbs L)Fe 2 Zn(μ 3 -NAr)(py). The two imido species were separated via crystallization, and outer sphere reduction of ( tbs L)Fe 2 Zn(μ 3 -NAr)(py) resulted in the formation of a single product, [2,2,2-crypt(K)][( tbs L)Fe 2 Zn(μ 3 -NAr)]. These results provide insight into the relationship between heterometallic cluster structure and substitutional lability and could help inform both future catalyst design and our understanding of metal atom lability in bioinorganic systems. Metal atom lability from a well-defined bimetallic cluster was canvassed as a function of ligand substitution, redox chemistry, and group transfer processes.