Bi- and Trimetallic σ-Acetylide Complexes Connected through a Phenyl Ring in the Fe(Cp*)(dppe) Series

Treatment of 1 equiv of the 1,3-bis(trimethylsilylethynyl)benzene with 2.3 equiv of [Fe(Cp*)(dppe)Cl] [ 1, Cp* = η 5 -C 5 Me 5, dppe = η 2 -bis(diphenylphosphino)ethane], KF and KPF 6 salts in a methanol/THF mixture (10:1) produced the bis(iron) alkyne complex [{Fe(Cp*)(η 2 -dppe)(C⋮C−)} 2 (1,3-C 6 H 4 )] ( 2 ) in 80% yield. Similarly, the trinuclear iron derivative [{Fe(Cp*)(η 2 -dppe)(C⋮C−)} 3 (1,3,5-C 6 H 3 )] ( 3 ) was obtained from reaction of 1 with 1,3,5-tris(trimethylsilylethynyl)benzene (80% yield with respect to the organic ligand). The X-ray crystal structure of 3 shows that it crystallizes in the triclinic space group with unit-cell parameters of a = 18.142(6) Å, b = 18.652(8) Å, c = 20.108(6) Å, α = 113.72(3), β = 89.87(3), γ = 116.07(3)°, and Z = 2. The structure was solved and refined (6922 reflections) to the final values R = 0.081 and R w = 0.069. Cyclic voltammetric analysis of complexes 2 and 3 from −1.0 to +0.5 V displays two and three one-electron reversible oxidation waves, respectively. The redox processes are all separated by 0.130 ± 0.010 V, indicating significant electronic communication between the metal centers. A theoretical treatment using density functional molecular orbital calculations has been made on compounds 2, 3, and the related compound [{Fe(Cp*)(η 2 -dppe)(C⋮C−)} 2 (1,4-C 6 H 4 )]. These results verify the experimental structure of 3 and allow an interpretation of its electronic structure.