Homoleptic hexa- and penta-coordinated gallium(I) amide complexes of ruthenium and molybdenum.

Reaction of neutral olefin complexes of ruthenium and molybdenum with GaTMP (TMP = 2,2,6,6-tetramethylpiperidinyl) by substitution leads to the formation of respective five- and six-coordinated homoleptic products. [Ru(GaTMP)5] (1) and [Mo(GaTMP)6] (2) were isolated and characterized. Core structure geometries were analyzed using continuous shape measure, and the complexes were subjected to DFT calculations unveiling competing π-interactions between the transition metal center and the amido substituent with the unoccupied pπ orbitals of the gallium.