一种混合甲基-氨基苄基胍基镥配合物对PrNCNPr、CS和PhPH的反应活性。

Reactivity of a mixed methyl-aminobenzyl guanidinate lutetium complex towards PrNCNPr, CS and PhPH.

作者信息

Jiang Wen, Zhang Lijun, Zhang Lixin

机构信息

Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Jiangwan Campus, Fudan University, Shanghai 200438, China.

Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Laboratory of Molecule-Based Materials, College of Chemistry and Materials Science, Anhui Normal University, Wuhu, Anhui 241000, China.

出版信息

Dalton Trans. 2022 Aug 23;51(33):12650-12660. doi: 10.1039/d2dt02008d.

DOI:10.1039/d2dt02008d

PMID:35930407

Abstract

A heteroleptic terminal alkyl lutetium complex stabilized by a bulky guanidinato ligand, LLu(CHCHNMe-)(Me)(THF) (1) (L = (PhCH)NC(NCHPr-2,6)) has been synthesized by the treatment of LLu(CHCHNMe-) with AlMe (1 equiv.) an alkyl-exchange reaction in toluene/THF (4 : 1) solution and fully characterized. The difference in the activities of aminobenzyl and methyl was also proven through their selective reactivity, including complex 1 with one equivalent of DIC, CS and HPPh, to afford complexes LLu(NPr)CMe (2), LLu[μ-η:η-SCCHCHNMe-]μ-η:η-SCCHCHNMe- (4), and {LLu(Me)[μ-O(CH) PPh]} (5), respectively. The subsequent transformations have also been investigated, obtaining complexes LLu[(NPr)CMe][(NPr)C CHCHNMe-] (3), {LLu[O(CH)PPh][μ-O(CH)PPh]} (6) and dimeric lutetium phosphide {LLu[μ-O(CH)PPh]}(Me)(PPh) (7). In addition, the guanidinate bimetallic alkynyl-bridged lutetium complex LLu(μ-CCPh) (8) bearing the μ-butatrienediyl group was obtained from the reaction of 1 with PhCCH (2 equiv.). The guanidinate lutetium μ-imido complex [LLu(μ-NPh)(THF)] (10) was also obtained in good yield by the treatment of 1 with PhNH.

摘要

一种由庞大的胍基配体稳定的杂配末端烷基镥配合物LLu(CHCHNMe-)(Me)(THF) (1)（L = (PhCH)NC(NCHPr-2,6)），通过在甲苯/四氢呋喃（4∶1）溶液中用AlMe（1当量）处理LLu(CHCHNMe-)经烷基交换反应合成，并进行了全面表征。氨基苄基和甲基活性的差异也通过它们的选择性反应得以证明，包括配合物1与1当量的DIC、CS和HPPh反应，分别得到配合物LLu(NPr)CMe (2)、LLu[μ-η:η-SCCHCHNMe-]μ-η:η-SCCHCHNMe- (4)和{LLu(Me)[μ-O(CH) PPh]} (5)。还研究了后续转化，得到配合物LLu[(NPr)CMe][(NPr)C CHCHNMe-] (3)、{LLu[O(CH)PPh][μ-O(CH)PPh]} (6)和二聚体镥磷化物{LLu[μ-O(CH)PPh]}(Me)(PPh) (7)。此外，带有μ-丁三烯二基的胍基双金属炔基桥联镥配合物LLu(μ-CCPh) (8)由1与PhCCH（2当量）反应制得。通过用PhNH处理1，还以良好产率得到了胍基镥μ-亚氨基配合物[LLu(μ-NPh)(THF)] (10)。