The use of [Cp '' Zr-2(eta(1:1)-E-4)] (E=P (1 a), As (1 b), Cp ''=1,3-di-tert-butyl-cyclopentadienyl) as phosphorus or arsenic source, respectively, gives access to novel stable polypnictogen transition metal complexes at ambient temperatures. The reaction of 1 a/1 b with [Cp(R)NiBr](2) (Cp(R)=Cp-Bn (1,2,3,4,5-pentabenzyl-cyclopentadienyl), Cp ''' (1,2,4-tri-tert-butyl-cyclopentadienyl)) was studied, to yield novel complexes depending on steric effects and stoichiometric ratios. Besides the transfer of the complete E-n unit, a degradation as well as aggregation can be observed. Thus, the prismane derivatives [(Cp ''' Ni)(2)(mu,eta(3:3)-E-4)] (2 a (E=P); 2 b (E=As)) or the arsenic containing cubane [(Cp ''' Ni)(3)(mu(3)-As)(As-4)] (5) are formed. Furthermore, the bromine bridged cubanes of the type [(Cp(R)Ni)(3){Ni(mu-Br)}(mu(3)-E)(4)](2) (Cp(R)=Cp ''': 6 a (E=P), 6 b (E=As), Cp(R)=Cp-Bn: 8 a (E=P), 8 b (E=As)) can be isolated. Here, a stepwise transfer of E-n units is possible, with a cyclo-E-4(2-) ligand being introduced and unprecedented triple-decker compounds of the type [{(Cp(R)Ni)(3)Ni(mu(3)-E)(4)}(2)(mu,eta(4:4)-E '(4))] (Cp(R)=Cp-Bn, Cp '''; E/E '=P, As) are obtained.