Conversion of E (E =P , As , AsP ) 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 Ni) tol] (1, L =[{N(C H Pr -2,6)C(Me)} CH] ) and [K ][(L Ni) (μ,η -N )] (6) were reacted with P , As and the interpnictogen compound AsP , respectively, yielding the homobimetallic complexes [(L Ni) (μ-η ,κ :η ,κ -E )] (E=P (2 a), As (2 b), AsP (2 c)), [(L Ni) (μ,η -E )] (E=P (3 a), As (3 b)) and [K@18-c-6(thf) ][L Ni(η -E )] (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 ][(L Ni) (μ,η -P )] (4) and [K@18-c-6(thf) ][(L Ni) (μ,η -E )] (E=P (5 a), As (5 b)), respectively. Compound 4 shows an unusual planarization of the initial Ni P -prism. All products were comprehensively characterized by crystallographic and spectroscopic methods.