Mund Garry, Vidovic Dragoslav, Batchelor Raymond J, Britten James F, Sharma Rajendra D, Jones Colin H W, Leznoff Daniel B
Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, BC V5A 1S6, Canada.
Chemistry. 2003 Oct 6;9(19):4757-63. doi: 10.1002/chem.200305014.
Several iron(III) complexes incorporating diamidoether ligands are described. The reaction between [Li(2)RN(SiMe(2))O] and FeX(3) (X=Cl or Br; R=2,4,6-Me(3)Ph or 2,6-iPr(2)Ph) form unusual ate complexes, FeX(2)LiRN(SiMe(2))O (2, X=Cl, R=2,4,6-Me(3)Ph; 3, X=Br, R=2,4,6-Me(3)Ph; 4, X=Cl, R=2,6-iPr(2)Ph) which are stabilized by Li-pi interactions. These dimeric iron(III)-diamido complexes exhibit magnetic behaviour characteristic of uncoupled high spin (S= 5/2 ) iron(III) centres. They also undergo halide metathesis resulting in reduced iron(II) species. Thus, reaction of 2 with alkyllithium reagents leads to the formation of iron(II) dimer FeMe(3)PhN(SiMe(2))O (6). Similarly, the previously reported iron(III)-diamido complex FeCltBuN(SiMe(2))O (1) reacts with LiPPh(2) to yield the iron(II) dimer FetBuN(SiMe(2))O but reaction with LiNPh(2) gives the iron(II) product [Fe(2)(NPh(2))(2)tBuN(SiMe(2))O] (5). Some redox chemistry is also observed as side reactions in the syntheses of 2-4, yielding THF adducts of FeX(2): the one-dimensional chain FeBr(2)(THF)(2) (7) and the cluster [Fe(4)Cl(8)(THF)(6)]. The X-ray crystal structures of 3, 5 and 7 are described.
描述了几种含有二酰胺醚配体的铁（III）配合物。[Li₂[RN(SiMe₂)₂]O]与FeX₃（X = Cl或Br；R = 2,4,6-Me₃Ph或2,6-iPr₂Ph）之间的反应形成了不寻常的铝酸盐配合物[FeX₂Li[RN(SiMe₂)₂]O]₂（2，X = Cl，R = 2,4,6-Me₃Ph；3，X = Br，R = 2,4,6-Me₃Ph；4，X = Cl，R = 2,6-iPr₂Ph），它们通过Li-π相互作用得以稳定。这些二聚体铁（III）-二酰胺配合物表现出未偶合的高自旋（S = 5/2）铁（III）中心的磁行为特征。它们还会发生卤化物复分解反应，生成低价铁（II）物种。因此，2与烷基锂试剂反应会生成铁（II）二聚体[Fe[Me₃PhN(SiMe₂)₂]O]₂（6）。类似地，先前报道的铁（III）-二酰胺配合物[FeCl[tBuN(SiMe₂)₂]O]₂（1）与LiPPh₂反应生成铁（II）二聚体[Fe[tBuN(SiMe₂)₂]O]₂，但与LiNPh₂反应则生成铁（II）产物[Fe₂(NPh₂)₂[tBuN(SiMe₂)₂]O]（5）。在2 - 4的合成过程中还观察到一些作为副反应的氧化还原化学现象，生成了FeX₂的THF加合物：一维链状的[FeBr₂(THF)₂]ₙ（7）和簇合物[Fe₄Cl₈(THF)₆]。描述了3、5和7的X射线晶体结构。
