posted on 2017-01-09, 15:18authored byMegan E. Reesbeck, Katarzyna Grubel, Daniel Kim, William W. Brennessel, Brandon Q. Mercado, Patrick L. Holland
The addition of (trimethylsilyl)diazomethane
and its conjugate base to iron β-diketiminate precursors gives
novel dinuclear complexes in which the bridges are either diazomethane
derivatives or an alkylidene. One product is an unusual bridging alkylidene
complex containing two three-coordinate iron(II) centers. On the other
hand, syntheses using the deprotonated diazomethane give two bridging
diazomethyl species with binding modes that have not been observed
in iron complexes previously. In the presence of a coordinating tetrahydrofuran
solvent, a diiron(II) compound with μ-N bridges rearranges to
a more stable isomer with μ-N,C bridges, a process that is accompanied
by a 1,3-shift of a silyl group.