Conversion of E4 (E4=P4, As4, AsP3) by Ni(0) and Ni(I) Synthons – A Comparative Study

Abstract

The reactivity of white phosphorus and yellow arsenic towards two different nickel nacnac complexes is investigated. The nickel complexes [(L1Ni)2tol] (1, L1=[{N(C6H3iPr2-2,6)C(Me)}2CH]−) and [K2][(L1Ni)2(μ,η1 : 1-N2)] (6) were reacted with P4, As4 and the interpnictogen compound AsP3, respectively, yielding the homobimetallic complexes [(L1Ni)2(μ-η2,κ1:η2,κ1-E4)] (E=P (2 a), As (2 b), AsP3 (2 c)), [(L1Ni)2(μ,η3 : 3-E3)] (E=P (3 a), As (3 b)) and [K@18-c-6(thf)2][L1Ni(η1 : 1-E4)] (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 [K2][(L1Ni)2(μ,η2 : 2-P4)] (4) and [K@18-c-6(thf)3][(L1Ni)2(μ,η3 : 3-E3)] (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.