Pyrrolide-ligated organoyttrium complexes. Synthesis, characterization, and lactide polymerization behavior

doi:10.1021/om060781y

CORC > 化学研究所 > 中国科学院化学研究所

	Pyrrolide-ligated organoyttrium complexes. Synthesis, characterization, and lactide polymerization behavior
	Yang, Yi ; Li, Shihui ; Cui, Dongmei ; Chen, Xuesi ; Jing, Xiabin
刊名	ORGANOMETALLICS
	2007-01-29
卷号	26 期号:3 页码:671-678
ISSN号	0276-7333
DOI	10.1021/om060781y
英文摘要	The N,N-bidentate ligand 2-{(N-2,6-diisopropylphenyl)iminomethyl)}pyrrole (L-1) and the N,N,P-tridentate ligand 2-{(N-2-diphenylphosphinophenyl)iminomethyl)}pyrrole (L-2) have been prepared. Their reactions with homoleptic yttrium tris(alkyl) compound Y(CH2SiMe3)(3)(THF)(2) have been investigated. Treatment of Y(CH2SiMe3)(3)(THF)(2) with 1 equiv of L-1 generated a THF-solvated bimetallic (pyrrolylaldiminato)yttrium mono(alkyl) complex (1) of central symmetry. In this process, L-1 is deprotonated by metal alkyl and its imino CN group is reduced to C-N by intramolecular alkylation, generating dianionic species that bridge two yttrium alkyl units in a unique eta(5)/eta(1):kappa(1) mode. The pyrrolyl ring behaves as a heterocyclopentadienyl ligand. Reaction of Y(CH2SiMe3)(3)(THF)(2) with 2 equiv of L-1 afforded the monomeric bis(pyrrolylaldiminato)yttrium mono(alkyl) complex (2), selectively. Amination of 2 with 2,6-diisopropylaniline gave the corresponding yttrium amido complex (3). In 3 the pyrrolide ligand is monoanionic and bonds to the yttrium atom in a eta(1):kappa(1) mode. The homoleptic tris(eta(1):kappa(1)-pyrrolylaldiminato)yttrium complex (4) was isolated when the molar ratio of L-1 to Y(CH2SiMe3)(3)(THF)(2) increases to 3:1. Reaction of L-2 with equimolar Y(CH2SiMe3)(3)(THF)(2) afforded an asymmetric binuclear complex (5). The dianionic N,N,P tridentate moieties derived from L-2 coordinate to yttrium atoms in eta(5)/eta(1):kappa(2) modes, generating tetrahedron and trigonal/pyramidal geometry around the two metal centers, respectively. Both alkylation of the imino CN group of ligand L-2 and the pyrrole's ability to act similar to a heterocyclopentadienyl moiety were also found in complex 5. Complexes 1-3 and 5 initiated polymerizations of D,L-lactide to give atactic polylactides with high molecular weights and narrow molecular weight distributions.
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000243577000029
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/62025]
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 Sch, Beijing 130039, Peoples R China
推荐引用方式 GB/T 7714	Yang, Yi,Li, Shihui,Cui, Dongmei,et al. Pyrrolide-ligated organoyttrium complexes. Synthesis, characterization, and lactide polymerization behavior[J]. ORGANOMETALLICS,2007,26(3):671-678.
APA	Yang, Yi,Li, Shihui,Cui, Dongmei,Chen, Xuesi,&Jing, Xiabin.(2007).Pyrrolide-ligated organoyttrium complexes. Synthesis, characterization, and lactide polymerization behavior.ORGANOMETALLICS,26(3),671-678.
MLA	Yang, Yi,et al."Pyrrolide-ligated organoyttrium complexes. Synthesis, characterization, and lactide polymerization behavior".ORGANOMETALLICS 26.3(2007):671-678.