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

The salt elimination reaction between FeCl2(THF)1.5 and the sterically hindered thallium tert-butyl-tris(3-isopropylpyrazolyl)borate, Tl[t-BuTpi-Pr], affords the new air and moisture-sensitive, high-spin, four-coordinate complex Fe[t-BuTpi-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-BuTpi-Pr]Cl is monomeric, and the homoscorpionate ligand is κ3-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-BuTpi-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-BuTpi-Pr]X (X = Et, Cl, Br), resulting formally from a facile and quantitative replacement of the [Fe–Cl]+ fragment by [Mg–X]+.

The salt elimination reaction between FeCl2(THF)1.5 and the sterically hindered thallium tert-butyl-tris(3-isopropylpyrazolyl)borate affords the new air and moisture-sensitive, high-spin, four-coordinate complex, Fe[t-BuTpi-Pr]Cl. The X-ray crystal structure determination shows (i) its monomeric nature, (ii) the κ3-coordination mode of the homoscorpionate ligand, and (iii) the trigonally distorted tetrahedral environment of the ferrous ion.Figure optionsDownload as PowerPoint slide