Reesbeck Megan E, Grubel Katarzyna, Kim Daniel, Brennessel William W, Mercado Brandon Q, Holland Patrick L
Department of Chemistry, Yale University , 225 Prospect Street, New Haven, Connecticut 06520, United States.
Department of Chemistry, University of Rochester , 120 Trustee Road, Rochester, New York 14627, United States.
Inorg Chem. 2017 Feb 6;56(3):1019-1022. doi: 10.1021/acs.inorgchem.6b01952. Epub 2017 Jan 9.
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.
将（三甲基硅基）重氮甲烷及其共轭碱添加到铁β-二酮亚胺前体中，得到了新型双核配合物，其中的桥连基团要么是重氮甲烷衍生物，要么是亚烷基。一种产物是一种不寻常的桥连亚烷基配合物，含有两个三配位铁（II）中心。另一方面，使用去质子化的重氮甲烷进行合成得到了两种桥连重氮甲基物种，其配位模式在铁配合物中此前未曾观察到。在配位性四氢呋喃溶剂存在下，一种具有μ-N桥的二价铁化合物重排为一种更稳定的具有μ-N,C桥的异构体，该过程伴随着一个硅基的1,3-迁移。
