Ruspic Christian, Spielmann Jan, Harder Sjoerd
Anorganische Chemie, Universität Duisburg-Essen, Universitätsstrasse 5-7, 45117 Essen, Germany.
Inorg Chem. 2007 Jun 25;46(13):5320-6. doi: 10.1021/ic700403d. Epub 2007 May 27.
The Yb(II) hydride complex (DIPP-nacnac)YbH x THF (3-Yb, DIPP-nacnac = CH{(CMe)(2,6-iPr(2)C(6)H(3)N)}(2)) was prepared by a mild metathesis reaction of (DIPP-nacnac)Yb[N(SiMe(3))(2)].THF with PhSiH(3). 3-Yb crystallizes as a dimer with bridging hydride ions, and its geometry is similar to that of the analogue calcium hydride complex (3-Ca). 3-Yb is well soluble in benzene and remarkably stable in solution at room temperature. Ligand exchange to the homoleptic Yb(II) complexes takes place at higher temperatures (3-Yb is less stable than the analogue 3-Ca). The soluble hydride complexes 3-Ca and 3-Yb are catalysts for the hydrosilylation of 1,1-diphenylethylene, but differences in the product distributions are observed. Slow hydrolysis of (DIPP-nacnac)Yb[N(SiMe(3))(2)].THF gave reduction of water and unidentified Yb(III) complexes. Fast hydrolysis at low temperature, however, resulted in the first Yb(II) hydroxide complex, (DIPP-nacnac)Yb(OH) x THF (4-Yb, 20% yield), which is a dimer with bridging hydroxide ions in the solid state. The crystal structure is isomorphous to that of the calcium analogue 4-Ca. 4-Yb is well soluble in benzene and considerably more stable against ligand exchange and formation of homoleptic species than 3-Yb.
通过（DIPP - nacnac）Yb[N(SiMe₃)₂]·THF与PhSiH₃的温和复分解反应制备了氢化镱配合物（DIPP - nacnac）YbH·THF（3 - Yb，DIPP - nacnac = CH{(CMe)(2,6 - iPr₂C₆H₃N)}₂）。3 - Yb以含有桥连氢负离子的二聚体形式结晶，其几何结构与类似的氢化钙配合物（3 - Ca）相似。3 - Yb可很好地溶于苯，并且在室温下在溶液中非常稳定。在较高温度下会发生配体交换生成同配体Yb(II)配合物（3 - Yb比类似物3 - Ca稳定性差）。可溶性氢化配合物3 - Ca和3 - Yb是1,1 - 二苯乙烯硅氢化反应的催化剂，但观察到产物分布存在差异。（DIPP - nacnac）Yb[N(SiMe₃)₂]·THF的缓慢水解导致水被还原并生成未鉴定的Yb(III)配合物。然而，在低温下快速水解得到了首个氢氧化镱配合物（DIPP - nacnac）Yb(OH)·THF（4 - Yb，产率20%），它在固态时是含有桥连氢氧根离子的二聚体。其晶体结构与钙类似物4 - Ca同构。4 - Yb可很好地溶于苯，并且相对于3 - Yb而言，在配体交换和生成同配体物种方面更稳定得多。
