The reactivity of white phosphorus and yellow arsenic towards two different nickel nacnac complexes is investigated. The nickel complexes [((LNi)-Ni-1)(2)tol] (1, L-1=[{N((C6H3Pr2)-Pr-i-2,6)C(Me)}(2)CH](-)) and [K-2][((LNi)-Ni-1)(2)(mu,eta(1 : 1)-N-2)] (6) were reacted with P-4, As-4 and the interpnictogen compound AsP3, respectively, yielding the homobimetallic complexes [((LNi)-Ni-1)(2)(mu-eta(2),kappa(1):eta(2),kappa(1)-E-4)] (E=P (2 a), As (2 b), AsP3 (2 c)), [((LNi)-Ni-1)(2)(mu,eta(3 : 3)-E-3)] (E=P (3 a), As (3 b)) and [K@18-c-6(thf)(2)][(LNi)-Ni-1(eta(1 : 1)-E-4)] (E=P (7 a), As (7 b)), respectively. Heating of 2 a, 2 b or 2 c also leads to the formation of 3 a or 3 b. Furthermore, the reactivity of these compounds towards reduction agents was investigated, leading to [K-2][((LNi)-Ni-1)(2)(mu,eta(2 : 2)-P-4)] (4) and [K@18-c-6(thf)(3)][((LNi)-Ni-1)(2)(mu,eta(3 : 3)-E-3)] (E=P (5 a), As (5 b)), respectively. Compound 4 shows an unusual planarization of the initial Ni2P4-prism. All products were comprehensively characterized by crystallographic and spectroscopic methods.