DABCO METALLOPORPHYRIN BINDING - TERNARY COMPLEXES, HOST GUEST CHEMISTRY, AND THE MEASUREMENT OF PI-PI-INTERACTIONS

被引：313

作者：

HUNTER, CA ^{[1
]}

MEAH, MN ^{[1
]}

SANDERS, JKM ^{[1
]}

机构：

[1] UNIV CAMBRIDGE,CTR MOLEC RECOGNIT,CHEM LAB,LENSFIELD RD,CAMBRIDGE CB2 1EW,ENGLAND

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1990年 / 112卷 / 15期

关键词：

D O I：

10.1021/ja00171a016

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Transient ternary complexes of the general form metalloporphyrin-DABCO-metalloporphyrin are described and characterized by NMR spectroscopy: the protons of DABCO (1,4-diazobicyclo[2.2.2]octane) molecules sandwiched between two diamagnetic metalloporphyrins resonate around -5 ppm. The same structural motif is shown to occur when DABCO binds within the cavity of cofacial metalloporphyrin dimers. The kinetics and thermodynamics of intracavity binding were measured by electronic and NMR spectroscopy and lead to an estimate of 48 ◾ 10 kJ mol-1 (11.5 ◾ 2.4 kcal mol-1) for the enthalpy of the π-π interaction between two zinc porphyrin moieties. The mechanism of ligand exchange and isomer interconversion for one of the porphyrin dimers has also been elucidated. © 1990, American Chemical Society. All rights reserved.

引用

页码：5773 / 5780

页数：8

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