Senda Shunsuke, Ohki Yasuhiro, Hirayama Tomoko, Toda Daisuke, Chen Jing-Lin, Matsumoto Tsuyoshi, Kawaguchi Hiroyuki, Tatsumi Kazuyuki
Department of Chemistry, Graduate School of Science and Research Center for Materials Science, Nagoya University, Nagoya 464-8602, Japan.
Inorg Chem. 2006 Nov 27;45(24):9914-25. doi: 10.1021/ic0610132.
A series of [Tm(Me)M(mu-Cl)]2 and Tm(R)MCl (Tm(R) = tris(mercaptoimidazolyl)borate; R = Me, tBu, Ph, 2,6-iPr2C6H3 (Ar); M = Mn, Fe, Co, Ni) complexes have been prepared by treatment of NaTm(Me) or LiTm(R) with an excess amount of metal(II) chlorides, MCl2. Treatment of Tm(R)MCl (R = tBu, Ph, Ar) with NaI led to a halide exchange to afford Tm(R)MI. The molecular structures of [Tm(Me)M(mu-Cl)]2 (M = Mn, Ni), [Tm(Me)Ni(mu-Br)]2, Tm(tBu)MCl (M = Fe, Co), Tm(Ph)MCl (M = Mn, Fe, Co, Ni), Tm(Ar)MCl (M = Mn, Fe, Co, Ni), Tm(Ph)MI (M = Mn, Co), and Tm(Ar)MI (M = Fe, Co, Ni) have been determined by X-ray crystallography. The Tm(R) ligands occupy the tripodal coordination site of the metal ions, giving a square pyramidal or trigonal bipyramidal coordination geometry for Tm(Me)M(mu-Cl)]2 and a tetrahedral geometry for the Tm(R)MCl complexes, where the S-M-S bite angles are larger than the reported N-M-N angles of the corresponding hydrotris(pyrazolyl)borate (Tp(R)) complexes. Treatment of Tm(Ph)2Fe with excess FeCl2 affords Tm(Ph)FeCl, indicating that Tm(R)2M as well as Tm(R)MCl is formed at the initial stage of the reaction between MCl2 and the Tm(R) anion.
通过用过量的金属（II）氯化物MCl₂处理NaTm（Me）或LiTm（R），制备了一系列的[Tm（Me）M（μ-Cl）]₂和Tm（R）MCl（Tm（R）=三（巯基咪唑基）硼酸盐；R = Me、tBu、Ph、2,6-iPr₂C₆H₃（Ar）；M = Mn、Fe、Co、Ni）配合物。用NaI处理Tm（R）MCl（R = tBu、Ph、Ar）导致卤化物交换，得到Tm（R）MI。通过X射线晶体学确定了[Tm（Me）M（μ-Cl）]₂（M = Mn、Ni）、[Tm（Me）Ni（μ-Br）]₂、Tm（tBu）MCl（M = Fe、Co）、Tm（Ph）MCl（M = Mn、Fe、Co、Ni）、Tm（Ar）MCl（M = Mn、Fe、Co、Ni）、Tm（Ph）MI（M = Mn、Co）和Tm（Ar）MI（M = Fe、Co、Ni）的分子结构。Tm（R）配体占据金属离子的三脚架配位位点，对于[Tm（Me）M（μ-Cl）]₂给出四方锥或三角双锥配位几何结构，对于Tm（R）MCl配合物给出四面体几何结构，其中S-M-S咬角大于相应的氢三（吡唑基）硼酸盐（Tp（R））配合物报道的N-M-N角。用过量的FeCl₂处理Tm（Ph）₂Fe得到Tm（Ph）FeCl，表明在MCl₂与Tm（R）阴离子反应的初始阶段形成了Tm（R）₂M以及Tm（R）MCl。
