Mono{hydrotris(mercaptoimidazolyl)borato} complexes of manganese(II), iron(II), cobalt(II), and nickel(II) halides.
Mono{hydrotris(mercaptoimidazolyl)borato} complexes of manganese(II), iron(II), cobalt(II), and nickel(II) halides.
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DOI：
10.1021/ic0610132
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发表时间：
2006-10
影响因子：
4.6
通讯作者：
Shunsuke Senda;Y. Ohki;T. Hirayama;Daisuke Toda;Jinglin Chen;Tsuyoshi Matsumoto;H. Kawaguchi;K. Tatsumi
中科院分区：
文献类型：
--
作者：
Shunsuke Senda;Y. Ohki;T. Hirayama;Daisuke Toda;Jinglin Chen;Tsuyoshi Matsumoto;H. Kawaguchi;K. Tatsumi
通过用过量的金属氯化物MCl 2处理NaTm（Me）或LiTm（R）制备了一系列[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-iPr 2C 6 H3（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。用X射线晶体学方法测定了[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）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，给出Tm（Me）M（μ-Cl）]2的四方锥或三角双锥配位几何形状和Tm（R）MCl络合物的四面体几何形状，其中S-M-S咬合角大于相应的氢化三（吡唑基）硼酸盐（Tp（R））络合物的报道的N-M-N角。用过量的FeCl 2处理Tm（Ph）2Fe得到Tm（Ph）FeCl，表明Tm（R）2 M以及Tm（R）MCl在MCl 2和Tm（R）阴离子之间反应的初始阶段形成。
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.