Nacnac‐Cobalt‐Mediated P4 Transformations

A comparison of P4 activations mediated by low-valent β-diketiminato (L) cobalt complexes is presented. The formal Co0 source [K2 (L3 Co)2 (μ2 :η1 ,η1 -N2 )] (1) reacts with P4 to form a mixture of the monoanionic complexes [K(thf)6 ][(L3 Co)2 (μ2 :η4 ,η4 -P4 )] (2) and [K(thf)6 ][(L3 Co)2 (μ2 :η3 ,η3 -P3 )] (3). The analogue CoI precursor [L3 Co(tol)] (4 a), however, selectively yields the corresponding neutral derivative [(L3 Co)2 (μ2 :η4 ,η4 -P4 )] (5 a). Compound 5 a undergoes thermal P atom loss to form the unprecedented complex [(L3 Co)2 (μ2 :η3 ,η3 -P3 )] (6). The products 2 and 3 can be obtained selectively by an one-electron reduction of their neutral precursors 5 a and 6, respectively. The electrochemical behaviour of 2, 3, 5 a, and 6 is monitored by cyclic voltammetry and their magnetism is examined by SQUID measurements and the Evans method. The initial CoI -mediated P4 activation is not influenced by applying the structurally different ligands L1 and L2 , which is proven by the formation of the isostructural products [(LCo)2 (μ2 :η4 ,η4 -P4 )] [L=L3 (5 a), L1 (5 b), L2 (5 c)].