The Nitration of Nickel(II)-, and Copper(II)-complexes of Bis(salicylaldehyde)ethylenediimine

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概要

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• The M(Salen) complexes (where M=Ni<SUP>II</SUP>, Cu<SUP>II</SUP>, Co<SUP>II</SUP>-NO, and V<SUP>IV</SUP>O, and where Salen=bis(salicylaldehyde)-ethylenediiminato dianio) were reacted with nitric oxide in organic solvents in the air. The free ligand can only form a compound with the formula of SalenH<SUB>2</SUB>·2HNO<SUB>3</SUB>, while the complexes with M=Ni or Cu gave NO<SUB>2</SUB>-substituted complexes, M(5,5′-dinitro-Salen), in almost quantitative yields. In the cases of Co(Salen)NO and VO-(Salen), no substitution reaction on the phenyl ring took place, but they formed a nitric acid adduct, Co(Salen)NO·<I>n</I>HNO<SUB>3</SUB>·<I>n</I>H<SUB>2</SUB>O(<I>n</I>=1 and 2) and VO(Salen)·HNO<SUB>3</SUB>·H<SUB>2</SUB>O. The reactions are thought to proceed by means of a process involving a nitric acid. The reactivity of the Ni- and Cu-Salen complexes is explained in terms of a π-electron localization at the 5- and 5′-positions of the phenyl rings resulting from <I>d</I><SUB>π</SUB>→<I>p</I><SUB>π</SUB> back bonding. A lack of a similar substitution reaction in Co(NO)- and VO-Salen complexes is explained as being due to the lower stability in the metal-Salen bonding.

• 公益社団法人 日本化学会の論文

著者

• Tamaki Motonori

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

• Shinra Koichiro

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

• Masuda Isao

  Department of Chemistry, Faculty of Science, Fukuoka University

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• Kinetics of monomerization or polymerization reaction for bis(N-phenyl-salicylideneaminato)nickel(II) and bis(N-methylsalicylidene-aminato)nickel(II) in solid phase.
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• The Characterization of Oligomeric Iron(II)-tetraoxime Complexes
• Cyanoethylation of Copper, Nickel, and Palladium Glycinates
• The Effect of Axial Pyridine Ligands on the Charge Transfer Bands of trans-Bis(dimethylglyoximato)Cobalt(III) and -Iron(II) Complexes
• Peroxo-, Oxo-, and catena-Oxo-Manganese Complexes with N,N′-Ethylenebis(salicylideneimine) Analogues
• The Preparation of Bis(dimethylglyoximato)nitrosylcobalt(II) and its Conversion into the Nitro Complex
• Coordination structure of Cu2+ ion in highly concentrated aqueous CuBr2 solution, determined by X-ray diffraction analysis.

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