Sella Andrea, Brown Sarah E, Steed Jonathan W, Tocher Derek A
Department of Chemistry, Christopher Ingold Laboratories, University College London, 20 Gordon Street, London, WC1H 0AJ United Kingdom.
Inorg Chem. 2007 Mar 5;46(5):1856-64. doi: 10.1021/ic062370f. Epub 2007 Jan 24.
In this paper, we report the first examples of trispyrazolylmethane complexes of rare earths. Reaction of LnCl3 with Tpm* (tris(3,5-dimethylpyrazolyl)methane) in THF or acetonitrile gives good yields of the [Ln(Tpm*)Cl3] (Ln = Y, Ce, Nd, Sm, Gd, Yb). Tpm* adducts of the lanthanide triflates [Ln(Tpm*)(OTf)3(THF)] (Ln = Y, Ho, Dy) may also be prepared. The X-ray crystal structures of [Y(Tpm*)Cl3], [Sm(Tpm*)Cl3(THF)], and [Ln(Tpm*)(OTf)3(THF)] (Ln = Y, Ho) are reported. The halide/triflate complexes may be used to prepare the aryloxide complexes [Ln(Tpm*)(OArMe2)3] (Ln = Y, Nd, Sm, Yb; ArMe2 = C6H3-2,6-(CH3)2), which are fluxional in solution as a result of interactions between the Tpm* and the aryloxide groups. The structures of the Nd and Sm complexes have been determined. Finally, the reaction of [Nd(BH4)3(THF)3] with Tpm* in THF results in the displacement of two THF molecules to give [Nd(Tpm*)(BH4)3(THF)]. Infrared spectra are consistent with tridentate borohydride coordination. The X-ray structures of these compounds indicate that the Tpm* ligand is less strongly bound than its anionic trispyrazolylborate analogues.
在本文中，我们报道了稀土三吡唑甲烷配合物的首例。LnCl₃与Tpm*（三（3,5 - 二甲基吡唑基）甲烷）在四氢呋喃或乙腈中反应，能以良好产率得到[Ln(Tpm*)Cl₃]（Ln = Y、Ce、Nd、Sm、Gd、Yb）。镧系元素三氟甲磺酸盐的Tpm加合物[Ln(Tpm)(OTf)₃(THF)]（Ln = Y、Ho、Dy）也可制备。报道了[Y(Tpm*)Cl₃]、[Sm(Tpm*)Cl₃(THF)]和[Ln(Tpm*)(OTf)₃(THF)]（Ln = Y、Ho）的X射线晶体结构。卤化物/三氟甲磺酸盐配合物可用于制备芳氧基配合物[Ln(Tpm*)(OArMe₂)₃]（Ln = Y、Nd、Sm、Yb；ArMe₂ = C₆H₃ - 2,6 - (CH₃)₂），由于Tpm与芳氧基之间的相互作用，这些配合物在溶液中具有动态特性。已确定了Nd和Sm配合物的结构。最后，[Nd(BH₄)₃(THF)₃]与Tpm在四氢呋喃中反应导致两个四氢呋喃分子被取代，生成[Nd(Tpm*)(BH₄)₃(THF)]。红外光谱与三齿硼氢化物配位一致。这些化合物的X射线结构表明，Tpm*配体的结合力比其阴离子三吡唑基硼酸盐类似物弱。
