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题名: Oxidative demetalation of Fischer alkoxy carbene complexes with stoichiometric pyridine N-oxide and NaBH4-promoted demetalation of Fischer iminocarbene complexes with sulfur and selenium
作者: Zheng, Zhaoyan;  Chen, Jinzhu;  Yu, Zhengkun;  Han, Xiuwen
通讯作者: 余正坤
关键词: Fischer carbene ;  pyridine N-oxide ;  iminocarbene ;  sulfur ;  selenium
刊名: JOURNAL OF ORGANOMETALLIC CHEMISTRY
发表日期: 2006-08-15
DOI: 10.1016/j.jorganchem.2006.05.021
卷: 691, 期:17, 页:3679-3692
收录类别: SCI ;  IC ;  CCR
文章类型: Article
部门归属: 2,5
项目归属: 203,502
产权排名: 1;1
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Inorganic & Nuclear ;  Chemistry, Organic
研究领域[WOS]: Chemistry
英文摘要: Oxidation of Fischer alkoxy carbene complexes were systematically investigated with stoichiometric pyridine N-oxide (PNO) under mild conditions, forming ester products in good to excellent yields from the corresponding monocarbene complexes. Fischer alkoxy biscarbene complexes efficiently underwent stepwise oxidative demetalation under controlled conditions, resulting in ester-monocarbene and diester products, respectively. This oxidation protocol has demonstrated a generally efficient method to oxidize Fischer alkoxy carbene complexes under mild conditions, providing a new route to novel monocarbene complexes from Fischer biscarbene complexes. In the presence of NaBH4, reactions of Fischer iminocarbene complexes with elemental sulfur or selenium in ethanol at ambient temperature regioselectively afforded thione or selone complexes by insertion of a sulfur or selenium atom into the M=C bonds in Fischer carbene complexes, and metal-free selone was also obtained. The molecular structures of the iminocarbene complexes and selone derivatives were confirmed by X-ray crystallographic study. The NaBH4-promoted demetalation protocol suggests a potential new route to demetalate Fischer aminocarbene complexes. (c) 2006 Elsevier B.V. All rights reserved.
关键词[WOS]: TRANSITION-METAL-COMPLEXES ;  DIELS-ALDER REACTIONS ;  TUNGSTEN PENTACARBONYL GROUPS ;  LEWIS ACID CATALYSIS ;  ASYMMETRIC-SYNTHESIS ;  ORGANIC SYNTHESES ;  ALKENYLCARBENE COMPLEXES ;  SELECTIVE ISOMERIZATION ;  PHOTOCHEMICAL-REACTIONS ;  C BONDS
语种: 英语
原文出处: 查看原文
WOS记录号: WOS:000239833100017
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/97203
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Liaoning, Peoples R China

Recommended Citation:
Zheng, Zhaoyan,Chen, Jinzhu,Yu, Zhengkun,et al. Oxidative demetalation of Fischer alkoxy carbene complexes with stoichiometric pyridine N-oxide and NaBH4-promoted demetalation of Fischer iminocarbene complexes with sulfur and selenium[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY,2006,691(17):3679-3692.
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