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

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.