SYNTHESIS AND STRUCTURES OF IRON(II) ALKYL AND THIOLATE COMPOUNDS CONTAINING STERICALLY HINDERED N-FUNCTIONALIZED ALKYL LIGANDS

Iron(II) dialkyl compounds [FeR2] (R = C(SiMe3)2C5H4N-2 (1), C(Ph)(SiMe3)C5H4N-2 (2), CH(SiMe3)C9H6N-8 (4)) and [{Fe(CHSitBuMe2C5H4N-2)2}2] (3) have been prepared from the reaction of FeCl2 with the appropriate N-functionalized alkyllithium reagent in a 1:2 molar ratio. The monoalkylated iron(II) complex [Fe{CPhSiMe3C5H4N-2}(Cl)(TMEDA)] (5) has been prepared by treating FeCl2 with a stoichiometric amount of the organolithium reagent. X-ray analysis revealed that the alkyl ligands are bonded to the metal centers in a chelating manner in the mononuclear compounds 1 and 5, whereas in 3 one of the alkyl ligands forms an interligand bridge betwen the two iron centers. Compounds 1, 2, 4, and 5 have magnetic moments in the range 4.24−4.96 μB that are characteristic of a high-spin d6 electronic configuration with four unpaired electrons. The magnetic moment of the binuclear compound 3 is 2.92 μB per iron atom, apparently a consequence of antiferromagnetic coupling between the two metal centers. Subsequent reactio...