• Bulletin of the Korean Chemical Society
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• v.23 no.5
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• pp.708-714
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• 2002

The hexanuclear metallamacrocycles were observed repeatedly in various conditions including the presence of several different tricationic metal ions in the macrocyclic ring system and of the linear alkyl chains at the acyl site of N-acylsalicylhydrazide ligand, which contrasts to the formation of the decanuclear metallamacrocycle with bulkier side chains such as phenyl group at the acyl site of the ligand. We synthesized a series of metallamacrocycles in various solvents to find the relationship between the solvents and the nuclearity of the metallamacrocycles. Whether the solvents are sterically more demanding or not, the complexes formed kept the hexanuclear metallamacrocycle system.

• Bulletin of the Korean Chemical Society
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• v.28 no.11
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• pp.2009-2014
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• 2007

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.