A Mixed Aryl/Amide Complex of Iron(II)

Abstract The combined incorporation of a labile and a stabilizing ligand in a metal‐organic precursor is of interest for the synthesis of low valent ligated (hetero)metallic clusters. The heteroleptic aryl/amide iron (II) complex [Fe 2 (Mes) 2 (BTSA) 2 ] ( 1 ) was synthesized by equimolar mixing of [Fe 2 (Mes) 4 ] with [Fe 2 (BTSA) 4 ]. (VT)‐NMR‐, UV‐Vis‐ and SC‐XRD‐analysis combined with DFT calculations revealed a dimeric structure with terminal bis(trimethylsilyl)amide‐ and bridging mesityl‐ligands in solution and as well in the solid phase. The treatment of [Fe 2 (BTSA) 4 ] with the carbenoid group 13 metallo‐ligand GaCp* is known to yield simply adducts. In contrast, monitoring the reactions of [Fe 2 (Mes) 4 ] and [Fe 2 (Mes) 2 (BTSA) 2 ] ( 1 ) with GaCp* by liquid injection field desorption mass spectrometry (LIFDI‐MS) suggest formation of a broader variety of bimetallic Fe−Ga‐species with iron formally reduced to iron (I) or iron (0). However, the product distribution obtained using the heteroleptic compound 1 indicates combined reactivity of the homoleptic congeners by showing larger species with variations of Fe/Ga ratios towards the formation of Fe/Ga clusters. This blended behavior is assigned to the more labile mesityl ligand and the more stabilizing BTSA‐ligand.