Synthesis of Unsupported Ln–Ga Bonds by Salt Metathesis and Ga–Ga Bond Reduction
Synthesis of Unsupported Ln–Ga Bonds by Salt Metathesis and Ga–Ga Bond Reduction
复制标题
DOI：
10.1021/om300309b
复制
发表时间：
2012-05
期刊：
影响因子：
2.8
通讯作者：
T. Sanden;M. T. Gamer;A. A. Fagin-A.;V. Chudakova;S. Konchenko;I. Fedushkin;P. Roesky
中科院分区：
文献类型：
--
作者：
T. Sanden;M. T. Gamer;A. A. Fagin-A.;V. Chudakova;S. Konchenko;I. Fedushkin;P. Roesky
报道了三种稀土配合物[{(DIPP-Bian)Ga}2LN(THf)4](Ln=Sm，Eu，Yb；DIPP-Bian=1，2-bis[(2，6-diisopropylphenyl)imino]acenaphthene)，)，它们的稀土原子只由两个{(DIPP-Bian)Ga}−和THf配位。在每个化合物中都发现了两个无支撑的Ln-Ga键。通过两条合成途径得到了稀土配合物：(1)将稀土金属还原插入到[(dipp-bian)Ga}]2的Ga-Ga键中；(2)[(dipp-bian)Gak(THF)5]与LnI2的盐异构化反应。此外，由SmI3和[(dipp-Bian)Gak(THF)5]通过还原反应还合成了化合物[{(dipp-Bian)Ga}2Sm(THF)4]。Ln-Ga键的长度强烈依赖于堆积效应。TmI_2(Thf)_5与[(dipp-Bian)Gak(Thf)_5]反应生成Tm(Ⅲ)配合物[{(dipp-Bian)Ga–Ga(dipp-Bian)}(C4H8O)TmI(thf)5]，，其中一个THF环被打开并还原两次，形成形式的双负电荷阴离子(O-CH_2-CH_2)_2-。这种稀土化合物..。
Three gallyl lanthanide complexes [{(dipp-Bian)Ga}2Ln(thf)4] (Ln = Sm, Eu, Yb; dipp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene), in which the lanthanide atoms are coordinated by only two {(dipp-Bian)Ga}− ligands and THF, are reported. Two unsupported Ln–Ga bonds are found in each compound. The gallyl lanthanide complexes have been obtained by two synthetic pathways: (1) reductive insertion of the lanthanide metals into the Ga–Ga bond of [{(dipp-Bian)Ga}]2 and (2) salt metathesis of [(dipp-Bian)GaK(thf)5] with LnI2. Moreover, the samarium compound [{(dipp-Bian)Ga}2Sm(thf)4] was additionally obtained in a reductive pathway from SmI3 and [(dipp-Bian)GaK(thf)5]. The length of the Ln–Ga bond strongly depends on packing effects. The reaction of TmI2(thf)5 and [(dipp-Bian)GaK(thf)5] gave the Tm(III) complex [{(dipp-Bian)Ga–Ga(dipp-Bian)}(C4H8O)TmI(thf)5], in which one THF ring was opened and reduced twice, forming the formal double negative charged anion (O-CH2-CH2-CH2-CH2)2–. This thulium compound...