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The reactivity of white phosphorus and yellow arsenic towards two different nickel nacnac complexes is investigated. The nickel complexes [(L 1 Ni) 2 tol] ( 1 , L 1 =[{N(C 6 H 3  i Pr 2 ‐2,6)C(Me)} 2 CH] − ) and [K 2 ][(L 1 Ni) 2 (μ,η 1 : 1 ‐N 2 )] ( 6 ) were reacted with P 4 , As 4  and the interpnictogen compound AsP 3 , respectively, yielding the homobimetallic complexes [(L 1 Ni) 2 (μ‐η 2 ,κ 1 :η 2 ,κ 1 ‐E 4 )] (E=P ( 2 a ), As ( 2 b ), AsP 3  ( 2 c )), [(L 1 Ni) 2 (μ,η 3 : 3 ‐E 3 )] (E=P ( 3 a ), As ( 3 b )) and [K@18‐c‐6(thf) 2 ][L 1 Ni(η 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 ][(L 1 Ni) 2 (μ,η 2 : 2 ‐P 4 )] ( 4 ) and [K@18‐c‐6(thf) 3 ][(L 1 Ni) 2 (μ,η 3 : 3 ‐E 3 )] (E=P ( 5 a ), As ( 5 b )), respectively. Compound  4  shows an unusual planarization of the initial Ni 2 P 4 ‐prism. All products were comprehensively characterized by crystallographic and spectroscopic methods.

Conversion of E 4 (E 4 =P 4 , As 4 , AsP 3 ) by Ni(0) and Ni(I) Synthons – A Comparative Study