Magnetic anisotropy in trigonal planar Fe(ii) bis(trimethylsilyl)amido complexes of the type [Fe{N(SiMe₃)₂}₂L]—experiment and theory

Abstract

The paper presents a combined experimental and theoretical study of the influence of the type of neutral ligand L on the electronic and magnetic properties of trigonal planar iron(ii) bis(trimethylsilyl)amido complexes [Fe(N(SiMe3)2L].

Molecular and Electronic Structures and Single-Molecule Magnet Behavior of Tris(thioether)–Iron Complexes Containing Redox-Active α-Diimine Ligands

“…Thus, these results demonstrate the potential for using strongly exchange-coupled nonbridging radical ligands to achieve slow magnetic relaxation in mononuclear transition metal complexes even when the magnetic anisotropy is relatively small. While a number of mononuclear iron complexes, including iron­(I), , iron­(II), − and iron­(III) complexes, − have been reported to exhibit SMM behavior, only one example besides complex 1 contains a radical ligand. In that case, the relaxation time was not reported due to the lack of a clear maximum in the out-of-phase AC susceptibility.…”

A “Solvent‐Free” Crystal Structure of [Fe{N(SiMe3)2}3] – Synthesis, Structure and Properties

“…However, in comparison to the original data of Bradley and coworkers [12] intensities are found to be 2 to 4 times higher which clearly suggests that the observed bands have to be assigned as ligand to metal charge transfer (LMCT) rather than spin forbidden d‐d transitions (Table 4). The spectra of concentrated solutions of 1 do not give evidences for d‐d bands in the NIR region characteristic for Fe 2+ compounds [8,9] which additionally indicates (in line with powder XRD and elemental analysis) that the amount of contamination, proven by Mößbauer spectroscopy, must be low.…”

“…Investigation of transition metal amides in our laboratory originally stems from the interest to utilize them as precursor complexes for the synthesis of mixed metal chalcogenide cluster complexes [5] and polymeric metal chalcogenolato complexes [6] . Recently, it also turned out that low coordinated metal complexes of type [Fe{N(SiMe 3 ) 2 } 2 L] (L=ligand) comprise interesting magnetic properties and can act as useful model complexes for the study of effects in the research area of single ion molecular magnetism [7,8,9] . For compounds with M 3+ =Sc, Ti, Cr, Fe, syntheses and properties have been described in the sixties and seventies by Bürger and Wannagat [10] as well as Bradley and coworkers [11,12,13,14] .…”

Lateral Metallation and Redistribution Reactions of Sodium Ferrates Containing Bulky 2,6‐Diisopropyl‐N‐(trimethylsilyl)anilide Ligands

“… [1] Amongst this family of compounds iron bis (amide) [Fe(HMDS) 2 ] 2 , having relatively basic bulky silylamido substituents, has become a versatile precursor to access a variety of Fe(II) compounds. Some of its applications include the fundamental exploration of its coordination chemistry and associated molecular magnetism,[ 2 , 3 , 4 , 5 , 6 , 7 ] the synthesis of hydride clusters,[ 8 , 9 ] hydrosilylation catalysis, [10] as well as emerging as an excellent precursor to access elusive low‐coordinate Fe(I) anionic species. [11] Exhibiting a dimeric solid‐state structure, [Fe(HMDS) 2 ] 2 exists as a linear two‐coordinate monomer in solution in non‐donor solvents at ambient temperature.…”