茂金属配合物中五甲基环戊二烯基配体的西格玛键复分解反应。（其中，M 为过渡金属）

Sigma bond metathesis with pentamethylcyclopentadienyl ligands in sterically crowded (C5Me5)3M complexes.

机构信息

Department of Chemistry, University of California, Irvine, California 92697-2025, USA.

出版信息

Dalton Trans. 2010 Aug 7;39(29):6767-73. doi: 10.1039/c002654a. Epub 2010 May 13.

PMID:20464027

Abstract

To further explore the reactivity of the (C(5)Me(5))(-) ligand in the sterically crowded (C(5)Me(5))(3)M complexes, reactions with PhEEPh (E = S, Se, Te) have been examined. With M = La, Pr, Nd, Sm, and Y, PhSSPh reacts to form the expected reduction products, (C(5)Me(5))(2)M(SPh), but the major organic byproduct is not the sterically induced reduction product, (C(5)Me(5))(2). Instead, the sigma bond metathesis product, C(5)Me(5)SPh, is the major byproduct. In contrast, reactions with (C(5)Me(5))(3)Ce and (C(5)Me(5))(3)U gave a mixture of C(5)Me(5)SPh and (C(5)Me(5))(2) as byproducts. PhSSPh reactions with the lanthanide nitrile adducts, (C(5)Me(5))(3)Ln(NCCMe(3))(2) (Ln = La, Ce) and (C(5)Me(5))(3)Nd(NCCMe(3)), formed (C(5)Me(5))(2)Ln(SPh)(NCCMe(3)) and only C(5)Me(5)SPh as the byproduct. PhSeSePh reactions paralleled the PhSSPh results, but reactions of PhTeTePh with (C(5)Me(5))(3)La, (C(5)Me(5))(3)Sm, and (C(5)Me(5))(3)La(NCCMe(3))(2) gave only (C(5)Me(5))(2) as a byproduct.

摘要

为了进一步探索在空间拥挤的 (C(5)Me(5))(3)M 配合物中 (C(5)Me(5))(-)配体的反应性，我们研究了与 PhEEPh（E = S、Se、Te）的反应。对于 M = La、Pr、Nd、Sm 和 Y，PhSSPh 反应生成预期的还原产物 (C(5)Me(5))(2)M(SPh)，但主要的有机副产物不是空间诱导的还原产物 (C(5)Me(5))(2)。相反，σ键复分解产物 C(5)Me(5)SPh 是主要的副产物。相比之下，与 (C(5)Me(5))(3)Ce 和 (C(5)Me(5))(3)U 的反应生成了 C(5)Me(5)SPh 和 (C(5)Me(5))(2)的混合物作为副产物。PhSSPh 与镧系元素腈加合物 (C(5)Me(5))(3)Ln(NCCMe(3))(2)（Ln = La、Ce）和 (C(5)Me(5))(3)Nd(NCCMe(3))反应生成 (C(5)Me(5))(2)Ln(SPh)(NCCMe(3))，仅 C(5)Me(5)SPh 作为副产物。PhSeSePh 的反应与 PhSSPh 的结果相似，但 PhTeTePh 与 (C(5)Me(5))(3)La、(C(5)Me(5))(3)Sm 和 (C(5)Me(5))(3)La(NCCMe(3))(2)的反应仅生成 (C(5)Me(5))(2)作为副产物。