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Synthesis, kinetics and mechanism of the reaction of a quasi‐aromatic copper(II) complex, [Cu(PnAO)‐6H] 0 , with aromatic aldehydes
Author(s) -
Wang ZhongMing,
Zhou ZhiFen,
Lin HuaKuan,
Zhu ShouRong,
Chen Yunti,
Jiang DongQing,
Murmann R. Kent
Publication year - 2000
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/1097-4601(20010101)33:1<1::aid-kin1>3.0.co;2-l
Subject(s) - chemistry , reaction rate constant , substituent , sn2 reaction , copper , kinetics , medicinal chemistry , ring (chemistry) , computational chemistry , organic chemistry , quantum mechanics , physics
The 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), was synthesized. Reactions of AH were studied spectrophotometrically in acidic media (pH = 1 ∼ 2, EtOH:H 2 O = 1:4 v/v) with para ‐substituted benzaldehydes (ald). The Cu,2N,3C quasi‐aromatic heterocyclic ring in AH is highly reactive at the central‐aromatic‐carbon atom, C12, to most aldehydes. A novel parallel, competitive and consecutive second‐order reaction mechanism is proposed. To obtain the rate constants following this mechanism, the Gauss‐Newton‐Marquardt and Runge‐Kutta methods were employed. Consistent results were obtained. Effects of acidity, solvent, temperature and substituent R (RH, CH 3 , OCH 3 , Cl) of the aromatic aldehydes on the reaction rate constants were studied. The results support the proposed SN2 mechanism. A linear free energy relationship between the rate constant k 1 and the Hammett parameters for the substituted benzaldehydes as well the activation parameters are presented. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 33: 1–8, 2001