Nickel-Triad Complexes of a Side-on Coordinating Distannene

NHC adducts of the stannylene Trip2Sn (Trip=2,4,6‐triisopropylphenyl) were reacted with zero‐valent Ni, Pd, and Pt precursor complexes to cleanly yield the respective metal complexes featuring a three‐membered ring moiety Sn‐Sn‐M along with carbene transfer onto the metal and complete substitution of the starting ligands. Thus the easily accessible NHC adducts to stannylenes are shown to be valuable precursors for transition‐metal complexes with an unexpected SnSn bond. The complexes have been studied by X‐ray diffraction and NMR spectroscopy as well as DFT calculations. The compounds featuring the structural motif of a distannametallacycle comprised of a [(NHC)2M0] fragment and Sn2Trip4 represent rare higher congeners of the well‐known olefin complexes. DFT calculations indicate the presence of a π‐type Sn–Sn interaction in these first examples for acyclic distannenes symmetrically coordinating to a zero‐valent transition metal. Differing analogues: On reacting the carbene adduct of the stannylene [Trip2Sn] (Trip=2,4,6‐triisopropylphenyl) with zero‐valent Group 10 complexes, symmetrically coordinating complexes of the distannene [Sn2Trip4] to Ni, Pd, and Pt have been obtained. Their structural and spectroscopic properties are presented and discussed.