期刊
INORGANIC CHEMISTRY
卷 57, 期 16, 页码 10442-10456出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.8b01701
关键词
-
资金
- NSF [DMR-1611250]
- NCN [OPUS 2015/17/B/ST5/02801]
- FNP [TEAM/2016-3/24]
Reactions of [closo-1-CB9H9-1-R](-) (2, R = H, COOH, C5H11) with PhI(OAc)(2) lead to mixtures of regioisomers [closo-1-CB9H8-1-R-6-IPh] (5[6]) and [closo-1-CB9H8-1-R-10-IPh] (5[10]) in ratios of similar to-3:1 to 1:1, of which the former isomer undergoes selective reactions with nucleophiles (MeCN, pyridine, MeC(=NH)NH2, CN-). The products and the unreacted 10-isomers 5[10] are separated achieving kinetic resolution of the isomeric iodonium zwitterions. Pure 5[10] is reacted with nucleophiles (pyridine, 4-C(7)H(15)OPyridine, Me2NCHS, PhCO2-, CN-, N-3(-), I-, MeC(=NH)NH2, and MeCN), giving substitution products. The mechanism of the substitution is investigated with density functional theory (DFT) methods. Some of the nucleophilic substitution products are transformed further, expanding the scope of available functional groups for the [closo-1-CB9H10](-) anion. Four derivatives are characterized with single-crystal XRD methods: [closo-1-CB9H9-10-N-2] (4[10]a), [closo-1-CB9H9-6-NC5H5] (9[6]a), [closo-1-CB9H9-10-NC5H5] (9[10]a), and [closo-1-CB9H9-10-NHC(NH2)Me] (10[10]a). Spectroscopic data for selected derivatives are interpreted in terms of transmission of electronic effects through the {closo-1-CB9} cluster (NMR) and interaction with substituents (IR, UV). The latter results are compared to those of TD-DFT computational methods.
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