Titanium and zirconium amido complexes supported by imidazole-containingligands: syntheses, characterization and catalytic activities

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	Titanium and zirconium amido complexes supported by imidazole-containingligands: syntheses, characterization and catalytic activities
	Zhao, Yang; Lin, Miaoshui; Chen, Zhou; Pei, Hao; Li, Yahong; Chen, Yanmei; Wang, Xiufang; Li, Lei; Cao, Yanyuan; Zhang, Yong; Li, Wu
	2012
发表期刊	RSC ADVANCES
ISSN	2046-2069
卷号	2 期号:1 页码:144-150
摘要	A series of new titanium and zirconium amido complexes, incorporating 4,5-diphenyl-2-(2-pyridinyl)-1H-imidazole (HL1), 4,5-bis(4-chlorophenyl)-2-(2-pyridinyl)-1H-imidazole (HL2), 4,5-bis(4-methoxyphenyl)-2-(2-pyridinyl)-1H-imidazole (HL3) and 4,5-bis(2-methoxyphenyl)-2-(2-pyridinyl)-1H-imidazole) (HL4) as the ancillary ligands, have been prepared and are shown to be pre-catalysts for the hydroamination of alkynes. Treatment of Ti(NMe2)(4) with 1 equivalent of HL1, HL2, HL3 and HL4, respectively, results in transamination with one dimethylamide group providing Ti(L1)(NMe2)(3) (1), Ti(L-2)(NMe2)(3) (2), Ti(L3)(NMe2)(3) (3), and Ti(L4)(NMe2)(3)center dot THF (4 center dot THF). Reaction of Ti(NMe2)(4) with 2 equivalents of HL1, HL2, HL3 and HL4, respectively, leads to production of titanium bisamido complexes Ti(L1)(2)(NMe2)(2 center dot)THF(5 center dot THF), Ti(L2)(2)(NMe2)(2)center dot THF (6 center dot THF), Ti(L3)(2)(NMe2)(2)center dot THF (7 center dot THF), and Ti(L-4)(2)(NMe2)(2) (8). Similarly, complexes Zr(L1)(NMe2)(3) (9), Zr(L1)(2)(NMe2)(2)center dot 1.5THF (10 center dot 1.5THF), Zr(L2)(2)(NMe2)(2)center dot 0.5THF (11 center dot 0.5THF), and Zr(L3)(2)(NMe2)(2)center dot 0.5THF (12 center dot 0.5THF) are generated by addition of 1 or 2 equivalents of the corresponding ligands to Zr(NMe2)(4). All compounds have been characterized by elemental and spectroscopic analyses. The solid-state structures of compounds 2 and 6 center dot THF have been further established by single X-ray diffraction analyses. The catalytic activities of 2 and 6 center dot THF towards the hydroamination of alkynes were explored. Complexes 2 and 6 center dot THF were found to be active pre-catalysts for the hydroamination reactions. Complex 2 showed higher catalytic activity and gave highly Markovnikov selective hydroamination of terminal alkynes. A series of new titanium and zirconium amido complexes, incorporating 4,5-diphenyl-2-(2-pyridinyl)-1H-imidazole (HL1), 4,5-bis(4-chlorophenyl)-2-(2-pyridinyl)-1H-imidazole (HL2), 4,5-bis(4-methoxyphenyl)-2-(2-pyridinyl)-1H-imidazole (HL3) and 4,5-bis(2-methoxyphenyl)-2-(2-pyridinyl)-1H-imidazole) (HL4) as the ancillary ligands, have been prepared and are shown to be pre-catalysts for the hydroamination of alkynes. Treatment of Ti(NMe2)(4) with 1 equivalent of HL1, HL2, HL3 and HL4, respectively, results in transamination with one dimethylamide group providing Ti(L1)(NMe2)(3) (1), Ti(L-2)(NMe2)(3) (2), Ti(L3)(NMe2)(3) (3), and Ti(L4)(NMe2)(3)center dot THF (4 center dot THF). Reaction of Ti(NMe2)(4) with 2 equivalents of HL1, HL2, HL3 and HL4, respectively, leads to production of titanium bisamido complexes Ti(L1)(2)(NMe2)(2 center dot)THF(5 center dot THF), Ti(L2)(2)(NMe2)(2)center dot THF (6 center dot THF), Ti(L3)(2)(NMe2)(2)center dot THF (7 center dot THF), and Ti(L-4)(2)(NMe2)(2) (8). Similarly, complexes Zr(L1)(NMe2)(3) (9), Zr(L1)(2)(NMe2)(2)center dot 1.5THF (10 center dot 1.5THF), Zr(L2)(2)(NMe2)(2)center dot 0.5THF (11 center dot 0.5THF), and Zr(L3)(2)(NMe2)(2)center dot 0.5THF (12 center dot 0.5THF) are generated by addition of 1 or 2 equivalents of the corresponding ligands to Zr(NMe2)(4). All compounds have been characterized by elemental and spectroscopic analyses. The solid-state structures of compounds 2 and 6 center dot THF have been further established by single X-ray diffraction analyses. The catalytic activities of 2 and 6 center dot THF towards the hydroamination of alkynes were explored. Complexes 2 and 6 center dot THF were found to be active pre-catalysts for the hydroamination reactions. Complex 2 showed higher catalytic activity and gave highly Markovnikov selective hydroamination of terminal alkynes.
语种	英语
文献类型	期刊论文
条目标识符	http://ir.isl.ac.cn/handle/363002/2083
专题	青海盐湖研究所知识仓储
推荐引用方式 GB/T 7714	Zhao, Yang,Lin, Miaoshui,Chen, Zhou,et al. Titanium and zirconium amido complexes supported by imidazole-containingligands: syntheses, characterization and catalytic activities[J]. RSC ADVANCES,2012,2(1):144-150.
APA	Zhao, Yang.,Lin, Miaoshui.,Chen, Zhou.,Pei, Hao.,Li, Yahong.,...&Li, Wu.(2012).Titanium and zirconium amido complexes supported by imidazole-containingligands: syntheses, characterization and catalytic activities.RSC ADVANCES,2(1),144-150.
MLA	Zhao, Yang,et al."Titanium and zirconium amido complexes supported by imidazole-containingligands: syntheses, characterization and catalytic activities".RSC ADVANCES 2.1(2012):144-150.

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