American Chemical Society
ic6b01952_si_005.cif (242 kB)

Diazoalkanes in Low-Coordinate Iron Chemistry: Bimetallic Diazoalkyl and Alkylidene Complexes of Iron(II)

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posted on 2017-01-09, 15:18 authored by Megan 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.