Synthesis, crystal structure, and reactivity of a four-coordinate iron(II) chloride complex bearing the sterically demanding tert-butyl-tris(3-isopropylpyrazolyl)borato ligand

Abstract

The salt elimination reaction between FeCl 2(THF) 1.5 and the sterically hindered thallium tert-butyl-tris(3-isopropylpyrazolyl)borate, Tl[ t-BuTp i-Pr ], affords the new air and moisture-sensitive, high-spin, four-coordinate complex Fe[ t-BuTp i-Pr ]Cl ( 1) in 52% yield. Compound 1 has been characterized by elemental analysis, paramagnetic 1H NMR, and X-ray crystal structure determination. Fe[ t-BuTp i-Pr ]Cl is monomeric, and the homoscorpionate ligand is κ 3-coordinated. The Fe(II) ion lies in a trigonally distorted tetrahedral environment with average N–Fe–N and N–Fe–Cl angles of 89.4(2)° and 125.7(2)°, respectively. Upon reactions with methyllithium followed by carbonylation, the six-coordinate acetyl-dicarbonyl derivative Fe[ t-BuTp i-Pr ](CO) 2{C( O)Me} was identified by IR spectroscopy. The reaction of 1 with ethylmagnesiumbromide furnished a mixture of mononuclear Grignard complexes Mg[ t-BuTp i-Pr ]X (X = Et, Cl, Br), resulting formally from a facile and quantitative replacement of the [Fe–Cl] + fragment by [Mg–X] +.