期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 137, 期 37, 页码 11872-11875出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.5b06973
关键词
-
资金
- U.S. NSF [CHE-0848248, CHE-1152123]
- University of Pennsylvania
- JSPS [12J03390]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1464659] Funding Source: National Science Foundation
The ethylene complex (PNP)Ti(eta(2)-H2C=CH2)((CH2Bu)-Bu-t) or (PNP)Ti=(CHBu)-Bu-t((CH2Bu)-Bu-t) (PNP- = N[2-P(CHMe2)(2)-4-methylphenyl](2)) reacts with H2CPPh3 to form the kappa(2)-phosphinoalkylidene (PNP)Ti= CHPPh2(Ph) (1). Compound 1 activates benzene via the transient intermediate [(PNP)Ti CPPh2] (C). By treatment of (PNP)Ti=(CHBu)-Bu-t(OTO with LiCH2PPh2, 1 or its isotopologue (PNP)Ti=CDPPh2(C6D5) (1-d(6)) can be produced by an independent route involving intermediate C, which activates benzene or benzene-d(6) and dehydrogenates cyclohexane-d(12). Addition of MeOTf to 1 results in elimination of benzene concomitant with the formation of the phosphonioalkylidyne complex, [(PNP)Ti=CPPh2Me(OTf) (2). Theoretical studies of 2 suggest a resonance structure having dominant Ti-C triple-bond character with some contribution also from a C-P multiple bond.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据