Preparation and X‐ray Crystal Structure of the First Trimeric Nickel Thiosemicarbazone Complex: The First Example of Oligomerization by both NiONi and NiSNi Bridging

Monomeric nickel(II) thiosemicarbazone complexes are an attractive new class of homogeneous catalysts for the activation of silanes. However, their activity is limited by the formation of inactive oligo‐ and polymers. The pathway by which aggregation takes place was elucidated by the preparation and X‐ray structural analysis of the first trimeric nickel(II) thiosemicarbazone complex. Aggregation was shown to proceed via NiONi and NiSNi bridging, giving rise to both fourfold planar and pseudooctahedral coordination of the nickel ions.