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Solvent Effect on the Nature of the Metallamacrocycles formed: Formation of Octanuclear and Dodecanuclear Manganese Metalladiazamacrocycles

Title
Solvent Effect on the Nature of the Metallamacrocycles formed: Formation of Octanuclear and Dodecanuclear Manganese Metalladiazamacrocycles
Author
나명수
Keywords
self-assembly; molecular polygon; octanuclear metallamacrocycle; dodecanuclear metallamacrocycle; solvent effect
Issue Date
2007-11
Publisher
KOREAN CHEMICAL SOC
Citation
BULLETIN OF THE KOREAN CHEMICAL SOCIETY, v. 28, No. 11, Page. 2009-2014
Abstract
The aminolysis of diphenyl thiophosphinic chloride (2) with substituted anilines in acetonitrile at 55.0 oC is investigated kinetically. Kinetic results yield large Hammett ρX (ρnuc = ?3.97) and Bronsted βX (βnuc = 1.40) values. A concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state is proposed on the basis of the primary normal kinetic isotope effects (kH/kD = 1.0-1.1) with deuterated aniline (XC6H4ND2) nucleophiles. The natural bond order charges on P and the degrees of distortion of 42 compounds: chlorophosphates [(R1O)(R2O)P(=O)Cl], chlorothiophosphates [(R1O)(R2O)P(=S)Cl], phosphonochloridates [(R1O)R2P(=O)Cl], phosphonochlorothioates [(R1O)R2P(=S)Cl], chlorophosphinates [R1R2P(=O)Cl], and chlorothiophosphinates [R1R2P(=S)Cl] are calculated at the B3LYP/ 6-311+G(d,p) level in the gas phase.
URI
http://www.koreascience.or.kr/article/JAKO200702727291444.pagehttps://repository.hanyang.ac.kr/handle/20.500.11754/107283
ISSN
1229-5949; 0253-2964
DOI
10.5012/bkcs.2007.28.11.2009
Appears in Collections:
COLLEGE OF SCIENCE AND CONVERGENCE TECHNOLOGY[E](과학기술융합대학) > ETC
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