Danopoulos Andreas A, Braunstein Pierre, Monakhov Kirill Yu, van Leusen Jan, Kögerler Paul, Clémancey Martin, Latour Jean-Marc, Benayad Anass, Tromp Moniek, Rezabal Elixabete, Frison Gilles
Institute for Advanced Study (USIAS), Université de Strasbourg, 67081 Strasbourg Cedex, France.
Université de Strasbourg, CNRS, CHIMIE UMR 7177, Laboratoire de Chimie de Coordination, Institut de Chimie, 4 rue Blaise Pascal, 67081 Strasbourg Cedex, France.
Dalton Trans. 2017 Jan 24;46(4):1163-1171. doi: 10.1039/c6dt03565e.
The linear, two-coordinate and isostructural heteroleptic [M(IPr){N(SiMe)}] (IPr = 1,3-bis(diisopropylphenyl)-imidazol-2-ylidene), formally M complexes (M = Co, 3; Fe, 4) were obtained by the reduction of [M(IPr)Cl{N(SiMe)}] with KC, or [Co(IPr){N(SiMe)}] with mesPH, mes = 2,4,6-tBuCH. The magnetism of 3 and 4 implies Co and Fe centres coupled to one ligand-delocalized electron, in line with XPS and XANES data; the ac susceptibility of 4 detected a pronounced frequency dependence due to slow magnetization relaxation. Reduction of [Fe(IPr)Cl{N(SiMe)}] with excess KC in toluene gave the heteronuclear 'inverse-sandwich' Fe-K complex 7, featuring η-toluene sandwiched between one Fe and one K centre.
通过用KC还原[M(IPr)Cl{N(SiMe)}]或用mesPH（mes = 2,4,6 - tBuCH）还原[Co(IPr){N(SiMe)}]，得到了线性、二维坐标且等结构的杂配[M(IPr){N(SiMe)}]（IPr = 1,3 - 双（二异丙基苯基）- 咪唑 - 2 - 亚基），形式上为M配合物（M = Co，3；Fe，4）。3和4的磁性表明Co和Fe中心与一个配体离域电子耦合，这与XPS和XANES数据一致；4的交流磁化率检测到由于缓慢的磁化弛豫而产生的明显频率依赖性。在甲苯中用过量的KC还原[Fe(IPr)Cl{N(SiMe)}]得到异核“反夹心”Fe - K配合物7，其特征是η - 甲苯夹在一个Fe和一个K中心之间。
