Cyclopentadienylaluminum thiolates - synthesis and structure

The dicyclopentadienylaluminum thiolates [Cp2Al(μ-SR)]2, where R = Et (1), iPr (2), were obtained by reacting Cl2AlSR with CpNa at the molar ratio 1:2, respectively. Use of CpLi leads to the formation of cyclopentadienyl(chloro)aluminum thiolates [Cp(Cl)Al(μ-SR)]2, exclusively, where R = Et (3), iPr (4), iBu (5), and nBu (6). The compounds were structurally characterized by multinuclear NMR and X-ray crystallography. The influence of steric and electronic factors on molecular structure, particularly on Cp-Al bond mode is discussed.