Kinetics and mechanism of the reaction of a quasi-aromatic copper(II) complex, [Cu(PnAO)-6H]0, with formaldehyde期刊界 All Journals 搜尽天下杂志传播学术成果专业期刊搜索期刊信息化学术搜索

Kinetics and mechanism of the reaction of a quasi-aromatic copper(II) complex, [Cu(PnAO)-6H]0, with formaldehyde

Authors:	Wang Zhong-Ming Lin Hua-Kuan Zhou Zhi-Fen Zhu Shou-Rong Chen Yun-Ti Murmann R. Kent

Affiliation:	(1) Department of Chemistry, Nankai University, Tianjin, 300071, P.R. China;(2) Department of Chemistry, University of Missouri, Columbia, MO 65211, USA

Abstract:	The kinetics of the reaction of CH₂O with a quasi-aromatic metal complex (1,1,2,8,9,9-hexamethyl-4,6-dioxa-5-hydro-3,7,10,14-tetraazacyclotetradecane-2,7,10,12-tetraene)copper(II), [Cu(PnAO)-6H]⁰ (AH), have been studied spectrophotometrically under neutral conditions in 1/3(v/v) MeOH–H₂O. The Cu, 2N, 3C quasi-aromatic heterocyclic ring in AH is highly reactive towards CH₂O at the central-aromatic-carbon atom, C(12) and the following reaction mechanism is proposed. ${text{AH + CH}}_{text{2}} {text{O}}xrightarrow{{{text{k}}_{text{1}} }}{text{A}}---{text{CH}}_{text{2}} OHxrightarrow[{ + AH}]{{k_2 }}A---CH_2 ---A$ ${text{A}}---{text{CH}}_{text{2}} ---{text{A + CH}}_{text{2}} O2A---CH_2 OH$ The compounds AH, A—CH₂OH and A—CH₂—A were isolated and identified by i.r spectroscopy and by elemental analysis. The kinetic data supported the proposed reaction sequence. All reactions were second order overall. The rate constants and corresponding activation parameters for every step were obtained and are discussed.

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