Department of Chemistry, Fudan University, Shanghai 200433, People's Republic of China.
Inorg Chem. 2009 Feb 16;48(4):1774-81. doi: 10.1021/ic802094q.
Reaction of Cp(2)LnCl with 1 equiv of KTp(Me2) in toluene gives the mixed Tp(Me2)/Cp lanthanide complexes Cp(2)Ln(Tp(Me2)) (Ln = Yb (1a), Er (1b), Dy (1c)), while unexpected complexes CpLn(Tp(Me2))Cl(THF) (Ln = Yb (2a), Er (2b.THF), Dy (2c), Y (2d)) are obtained when the reactions are carried out in THF. Complex 2b can also be formed by the reaction of CpErCl(2)(THF)(3) with 1 equiv of KTp(Me2) in THF. Moreover, complex 1a can also be obtained from the reaction of Cp(3)Yb and KTp(Me2). The results not only represent an efficient and versatile method for the synthesis of mixed Cp/Tp(Me2) lanthanide complexes but also provide new insight into the reactivity of Cp(2)LnCl. Furthermore, the reactivities of complexes 1a-c toward proton-donating reagents are examined. It has been found that 1b reacts with benzotriazole (C(6)H(4)NHN(2)) in THF to yield a lanthanide metallomacrocyclic complex (Tp(Me2))CpEr(mu-N(3)C(6)H(4)) (3), while the reaction of 1a with 1 equiv of 2-aminopyridine in THF gives an unexpected oxide complex (Tp(Me2))Yb(2-HNC(5)H(4)N)(mu-O) (4). Presumably, the oxide ligand of compound 4 results from adventitious water. In addition, treatment of 1c with 2 equiv of 3,5-dimethylpyrazole yields a completely Cp-abstracted product (Tp(Me2))Dy(Pz(Me2))(2)(THF) (5), which can also be directly obtained from a three-component reaction of Cp(2)DyCl, KTp(Me2), and 3,5-dimethylpyrazole in THF. These results further indicate that the new mixed Tp(Me2)/Cp lanthanide complexes are practical and versatile precursors for the synthesis of poly(pyrazolyl)borate lanthanide derivatives. All new compounds have been characterized by elemental analysis and spectroscopic methods. The structures of complexes 1a,b and 2-5 have also been determined through single-crystal X-ray diffraction analysis.
Cp(2)LnCl 与 1 当量的 KTp(Me2) 在甲苯中反应得到混合 Tp(Me2)/Cp 镧系元素配合物 Cp(2)Ln(Tp(Me2))（Ln = Yb（1a），Er（1b），Dy（1c）），而当反应在 THF 中进行时，却得到了意想不到的 CpLn(Tp(Me2))Cl(THF)（Ln = Yb（2a），Er（2b.THF），Dy（2c），Y（2d））配合物。配合物 2b 也可以通过 CpErCl(2)(THF)(3)与 1 当量的 KTp(Me2)在 THF 中的反应得到。此外，配合物 1a 也可以由 Cp(3)Yb 和 KTp(Me2)反应得到。这些结果不仅代表了一种高效、通用的合成混合 Cp/Tp(Me2)镧系元素配合物的方法，而且还提供了 Cp(2)LnCl 反应性的新见解。此外，还研究了配合物 1a-c 对供质子试剂的反应性。发现 1b 在 THF 中与苯并三唑（C(6)H(4)NHN(2)）反应生成镧系元素金属大环配合物(Tp(Me2))CpEr(mu-N(3)C(6)H(4))（3），而 1a 在 THF 中与 1 当量的 2-氨基吡啶反应得到意想不到的氧化物配合物(Tp(Me2))Yb(2-HNC(5)H(4)N)(mu-O)（4）。推测化合物 4 的氧化物配体是由偶然水引起的。此外，用 2 当量的 3,5-二甲基吡唑处理 1c 得到完全 Cp 被提取的产物（Tp(Me2))Dy(Pz(Me2))(2)(THF)（5），它也可以直接通过 Cp(2)DyCl、KTp(Me2)和 3,5-二甲基吡唑在 THF 中的三组分反应得到。这些结果进一步表明，新型混合 Tp(Me2)/Cp 镧系元素配合物是合成多（吡唑基）硼酸盐镧系元素衍生物的实用且通用的前体。所有新化合物均通过元素分析和光谱方法进行了表征。配合物 1a、b 和 2-5 的结构也通过单晶 X 射线衍射分析确定。
