Influence of the nacnac Ligand in Iron(I)-Mediated P4 Transformations

Abstract

A study of P4 transformations at low-valent iron is presented using β-diketiminato (L) Fe(I) complexes [LFe(tol)] (tol=toluene; L=L(1) (1 a), L(2) (1 b), L(3) (1 c)) with different combinations of aromatic and backbone substituents at the ligand. The products [(LFe)4 (μ4 -η(2) :η(2) :η(2) :η(2) -P8 )] (L=L(1) (2 a), L(2) (2 b)) containing a P8 core were obtained by the reaction of 1 a,b with P4 in toluene at room temperature. Using a slightly more sterically encumbered ligand in 1 c results in the formation of [(L(3) Fe)2 (μ-η(4) :η(4) -P4 )] (2 c), possessing a cyclo-P4 moiety. Compounds 2 a-c were comprehensively characterized and their electronic structures investigated by SQUID magnetization and (57) Fe Mössbauer spectroscopy as well as by DFT methods.

Keywords: Mössbauer spectroscopy; paramagnetic compounds; small-molecule activation; substituent effects; white phosphorus.