The synthesis, structural characterization, and bonding situation analysis of a novel, all-zinc, hepta-coordinated palladium complex [Pd(ZnCp*)(4)(ZnMe)(2){Zn(tmeda)}] (1) is reported. The reaction of the substitution labile d(10) metal starting complex [Pd(CH(3))(2)(tmeda)] (tmeda = N,N,N',N'-tetramethyl-ethane-1,2-diamine) with stoichiometric amounts of [Zn(2)Cp*(2)] (Cp* = pentamethylcyclopentadienyl) results in the formation of [Pd(ZnCp*)(4)(ZnMe)(2){Zn(tmeda)}] (1) in 35% yield. Compound 1 has been fully characterized by single-crystal X-ray diffraction, (1)H and (13)C NMR spectroscopy, IR spectroscopy, and liquid injection field desorption ionization mass spectrometry. It consists of an unusual [PdZn(7)] metal core and exhibits a terminal {Zn(tmeda)} unit. The bonding situation of 1 with respect to the properties of the three different types of Zn ligands Zn(R,L) (R = CH(3), Cp*; L = tmeda) bonded to the Pd center was studied by density functional theory quantum chemical calculations. The results of energy decomposition and atoms in molecules analysis clearly point out significant differences according to R vs L. While Zn(CH(3)) and ZnCp* can be viewed as 1e donor Zn(I) ligands, {Zn(tmeda)} is best described as a strong 2e Zn(0) donor ligand. Thus, the 18 valence electron complex 1 nicely fits to the family of metal-rich molecules of the general formula [M(ZnR)(a)(GaR)(b)] (a + 2b = n ≥ 8; M = Mo, Ru, Rh; Ni, Pd, Pt; R = Me, Et, Cp*).