The behavior of pyrrolyl ligands within the rare-earth metal alkyl complexes. Insertion of C=N and C=O double bonds into Ln-sigma-C bonds

doi:10.1039/b926038b

CORC > 化学研究所 > 中国科学院化学研究所

	The behavior of pyrrolyl ligands within the rare-earth metal alkyl complexes. Insertion of C=N and C=O double bonds into Ln-sigma-C bonds
	Yang, Yi 1,2; Cui, Dongmei 1; Chen, Xuesi 1
刊名	DALTON TRANSACTIONS
	2010
卷号	39 期号:16 页码:3959-3967
ISSN号	1477-9226
DOI	10.1039/b926038b
英文摘要	This paper presents some unusual reactions of lanthanide tris(alkyl)s or lanthanide mono-Cp' (Cp' = (C(5)Me(4))SiMe(3))bis(alkyl)s with pyrrolyl ligands, and the eta(5)- or eta(1)-coordination mode of the pyrrolyl ring, as well as C=N and C=O double bonds insertion into Ln-sigma-C moities. N, N, O-tridentate ligand HL(1), 2-(2-CH(3)OC(6)H(3)N=CH)-C(4)H(3)NH, was prepared. Treatment of HL(1) with rare-earth metal tris(alkyl)s, Ln(CH(2)SiMe(3))(3)(THF)(2), generated centrosymmetric bimetallic (pyrrolylaldiminato)lanthanide mono(alkyl) complexes [{2-(2-CH(3)OC(6)H(3)NC(H)R)-C(4)H(3)N}LnR](2) (1a: Ln = Y; 1b: Ln = Lu) (R = CH(2)SiMe(3)). In this process, HL(1) was deprotonated by the metal alkyl and its imino C=N group was deactivated by the intramolecular alkylation, generating dianionic species that bridged the two metal alkyl units in eta(5)/eta(1):kappa(1) modes. When the reaction was carried out in dimethoxyethane (DME), asymmetric complex [2-(2-CH(3)OC(6)H(3)NC(H)R)-C(4)H(3)N](2)Y(2)R(2)(DME) (2) was given. Furthermore, the reaction of alkyl complex 1b and benzophenone (Ph(2)C=O) afforded alkyl-insertion product [{2-(2-CH(3)OC(6)H(3)NC(H)R)-C(4)H(3)N}LuOC(R)Ph(2)](2) (3). Both the intermolecular alkylation and the pyrrole's behavior as the hetero-cyclopentadienyl ligand were also observed in complexes 2 and 3. HL(1) reacted with (eta(5)-Cp')Y(CH(2)SiMe(3))(2)(THF) (E) to form a mixed ligands supported alkyl complex [(eta(5)-Cp')(L(1))]Y(CH(2)SiMe(3))(THF) (4), whilst complex E was treated with 2-(2,6-iPr(2)C(6)H(3)N=CH)-C(4)H(3)NH (HL(2)) to yield [(eta(5)-Cp')(L(2))]Y(CH(2)SiMe(3))(THF) (5). However, reaction of E and 2-(Me(2)NCH(2))-C(4)H(3)NH (HL(3)) afforded Y[(eta(5)-Cp')(L(3))(2)] (6), and ligand redistribution was found in this process. The molecular structures of complexes 5 and 6 were confirmed by X-ray diffraction, which indicated that the C=N double bond survived and the pyrrolyl ring coordinated to the metal center in eta(1)-mode.
语种	英语
出版者	ROYAL SOC CHEMISTRY
WOS记录号	WOS:000276377100022
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/69341]
专题	中国科学院化学研究所
通讯作者	Cui, Dongmei
作者单位	1.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China 2.Chinese Acad Sci, Grad Univ, Beijing 100039, Peoples R China
推荐引用方式 GB/T 7714	Yang, Yi,Cui, Dongmei,Chen, Xuesi. The behavior of pyrrolyl ligands within the rare-earth metal alkyl complexes. Insertion of C=N and C=O double bonds into Ln-sigma-C bonds[J]. DALTON TRANSACTIONS,2010,39(16):3959-3967.
APA	Yang, Yi,Cui, Dongmei,&Chen, Xuesi.(2010).The behavior of pyrrolyl ligands within the rare-earth metal alkyl complexes. Insertion of C=N and C=O double bonds into Ln-sigma-C bonds.DALTON TRANSACTIONS,39(16),3959-3967.
MLA	Yang, Yi,et al."The behavior of pyrrolyl ligands within the rare-earth metal alkyl complexes. Insertion of C=N and C=O double bonds into Ln-sigma-C bonds".DALTON TRANSACTIONS 39.16(2010):3959-3967.