The dinuclear palladium(I) complexes [L(Ar2 HGe)Pd(μ-GeAr2 )2 Pd(GeHAr2 )L] (Ar=Ph, p-Tol; L=PMe3 , tBuNC) contain terminal germyl and bridging germylene ligands with the experimentally observed Ge⋅⋅⋅Ge bond lengths of 2.8263(4) Å (L=PMe3 ) and 2.928(1) Å (L=tBuNC), which are close to the longest Ge-Ge bond reported to date [2.714(1) Å]. Significant Ge⋅⋅⋅Ge interactions between the germylene and germyl ligands (PMe3 complexes > tBuNC complexes) are supported by DFT calculations, Wiberg bond indices (WBI), and natural bond orbital (NBO) analyses. Exchanging tBuNC for PMe3 ligands increases the Ge⋅⋅⋅Ge interaction, and simultaneously activates two Pd-Ge bonds. Adding the chelating diphosphine 1,2-bis(diethylphosphino)ethane (depe) to the PMe3 complexes results in the intramolecular coupling of germyl and germylene ligands followed by extrusion of a digermane.

A new triangular triplatinum(0) complex with bridging diphenylgermylene ligands, [{Pt(PMe3)}3(μ-GePh2)3], undergoes insertion of ZC≡CZ (Z = COOMe) into a Pt-Ge bond. The product contains a μ3-η(2)(∥)-CZ=CZ-GePh2 ligand on the Pt3 plane. Two molecules of HC≡CZ react to afford the Pt3 complex with chelating C, Ge- and Ge, Ge-ligands.

The dinuclear palladium(I) complexes [L(Ar2HGe)Pd(μ‐GeAr2)2Pd(GeHAr2)L] (Ar=Ph, p‐Tol; L=PMe3, tBuNC) contain terminal germyl and bridging germylene ligands with the experimentally observed Ge⋅⋅⋅Ge bond lengths of 2.8263(4) Å (L=PMe3) and 2.928(1) Å (L=tBuNC), which are close to the longest GeGe bond reported to date [2.714(1) Å]. Significant Ge⋅⋅⋅Ge interactions between the germylene and germyl ligands (PMe3 complexes > tBuNC complexes) are supported by DFT calculations, Wiberg bond indices (WBI), and natural bond orbital (NBO) analyses. Exchanging tBuNC for PMe3 ligands increases the Ge⋅⋅⋅Ge interaction, and simultaneously activates two PdGe bonds. Adding the chelating diphosphine 1,2‐bis(diethylphosphino)ethane (depe) to the PMe3 complexes results in the intramolecular coupling of germyl and germylene ligands followed by extrusion of a digermane.