Transesterification by (hydroxo)nickel(II) complex in the presence of external alcohol

Masami Ito, Ken Sakai, Taro Tsubomura, Yu Saku Takita

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Abstract

The nickel(II) complexes, [(tpa)Ni(II)(μ-OH)2Ni(II)(tpa)](ClO4)2 (tpa = tris(2-pyridylmethyl)amine) (2), [Ni(II)(CH3CN)(tpa)(H2O)](ClO4)2 (3) have been prepared and fully characterized. X-Ray crystallography of complex 2 and its methanol adduct, [(tpa)Ni(II)(μ- OH)2Ni(II)(tpa)](ClO4)2·2MeOH ((2)·2MeOH) revealed a molecular structure containing two Ni centers bridged by two OH ligands. The Ni-O distances in 2·2MeOH are longer than those in 2. The MeCN ligand in complex 3 is replaced by EtCN to give [Ni(II)(EtCN)(tpa)(H2O)](ClO4)2 (4), which was characterized by X-ray crystallography. The kinetic study of p-NPA (p- nitrophenyl acetate, 0.1, 0.5, 1 mM) hydrolysis by complex 2 (20, 10, 6 mM) was performed in the presence of ethanol (100 mM) in MeCN solution (1 M = 1 mol dm-3). By following the 400 nm absorption derived from p-nitrophenolate ion, we obtained the second-order kinetics; first-order in [2] and first- order in [p-NPA]. Addition of ethanol resulted in enhancement of the second- order rate constant (from 1.6x10-3 M-1 s-1 to 1.6x10-2 M-1 s-1 at 25°C) as well as formation of a transesterified product, ethyl acetate. The second-order rate constant of the reaction in the presence of added ethanol (0.016 M-1 s-1) at 25°C is much larger than that of the reaction without ethanol (0.0016 M-1 s-1). Also observed was a transesterified product, ethyl acetate, from the reaction of 2 with p-NPA in the presence of ethanol. The pK(a) value of the ligated water molecule in 3 was estimated to be 10.7 by kinetic measurements in 40% MeCN aqueous solution at 25°C, I = 0.3.

Original languageEnglish
Pages (from-to)239-247
Number of pages9
JournalBulletin of the Chemical Society of Japan
Volume72
Issue number2
DOIs
Publication statusPublished - Feb 1 1999

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Transesterification
Nickel
Ethanol
Alcohols
X ray crystallography
Kinetics
Rate constants
Ligands
Molecular structure
Methanol
Hydrolysis
Ions
Molecules
perchlorate
Water
4-nitrophenyl acetate
ethyl acetate

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Transesterification by (hydroxo)nickel(II) complex in the presence of external alcohol. / Ito, Masami; Sakai, Ken; Tsubomura, Taro; Takita, Yu Saku.

In: Bulletin of the Chemical Society of Japan, Vol. 72, No. 2, 01.02.1999, p. 239-247.

Research output: Contribution to journalArticle

Ito, Masami ; Sakai, Ken ; Tsubomura, Taro ; Takita, Yu Saku. / Transesterification by (hydroxo)nickel(II) complex in the presence of external alcohol. In: Bulletin of the Chemical Society of Japan. 1999 ; Vol. 72, No. 2. pp. 239-247.
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N2 - The nickel(II) complexes, [(tpa)Ni(II)(μ-OH)2Ni(II)(tpa)](ClO4)2 (tpa = tris(2-pyridylmethyl)amine) (2), [Ni(II)(CH3CN)(tpa)(H2O)](ClO4)2 (3) have been prepared and fully characterized. X-Ray crystallography of complex 2 and its methanol adduct, [(tpa)Ni(II)(μ- OH)2Ni(II)(tpa)](ClO4)2·2MeOH ((2)·2MeOH) revealed a molecular structure containing two Ni centers bridged by two OH ligands. The Ni-O distances in 2·2MeOH are longer than those in 2. The MeCN ligand in complex 3 is replaced by EtCN to give [Ni(II)(EtCN)(tpa)(H2O)](ClO4)2 (4), which was characterized by X-ray crystallography. The kinetic study of p-NPA (p- nitrophenyl acetate, 0.1, 0.5, 1 mM) hydrolysis by complex 2 (20, 10, 6 mM) was performed in the presence of ethanol (100 mM) in MeCN solution (1 M = 1 mol dm-3). By following the 400 nm absorption derived from p-nitrophenolate ion, we obtained the second-order kinetics; first-order in [2] and first- order in [p-NPA]. Addition of ethanol resulted in enhancement of the second- order rate constant (from 1.6x10-3 M-1 s-1 to 1.6x10-2 M-1 s-1 at 25°C) as well as formation of a transesterified product, ethyl acetate. The second-order rate constant of the reaction in the presence of added ethanol (0.016 M-1 s-1) at 25°C is much larger than that of the reaction without ethanol (0.0016 M-1 s-1). Also observed was a transesterified product, ethyl acetate, from the reaction of 2 with p-NPA in the presence of ethanol. The pK(a) value of the ligated water molecule in 3 was estimated to be 10.7 by kinetic measurements in 40% MeCN aqueous solution at 25°C, I = 0.3.

AB - The nickel(II) complexes, [(tpa)Ni(II)(μ-OH)2Ni(II)(tpa)](ClO4)2 (tpa = tris(2-pyridylmethyl)amine) (2), [Ni(II)(CH3CN)(tpa)(H2O)](ClO4)2 (3) have been prepared and fully characterized. X-Ray crystallography of complex 2 and its methanol adduct, [(tpa)Ni(II)(μ- OH)2Ni(II)(tpa)](ClO4)2·2MeOH ((2)·2MeOH) revealed a molecular structure containing two Ni centers bridged by two OH ligands. The Ni-O distances in 2·2MeOH are longer than those in 2. The MeCN ligand in complex 3 is replaced by EtCN to give [Ni(II)(EtCN)(tpa)(H2O)](ClO4)2 (4), which was characterized by X-ray crystallography. The kinetic study of p-NPA (p- nitrophenyl acetate, 0.1, 0.5, 1 mM) hydrolysis by complex 2 (20, 10, 6 mM) was performed in the presence of ethanol (100 mM) in MeCN solution (1 M = 1 mol dm-3). By following the 400 nm absorption derived from p-nitrophenolate ion, we obtained the second-order kinetics; first-order in [2] and first- order in [p-NPA]. Addition of ethanol resulted in enhancement of the second- order rate constant (from 1.6x10-3 M-1 s-1 to 1.6x10-2 M-1 s-1 at 25°C) as well as formation of a transesterified product, ethyl acetate. The second-order rate constant of the reaction in the presence of added ethanol (0.016 M-1 s-1) at 25°C is much larger than that of the reaction without ethanol (0.0016 M-1 s-1). Also observed was a transesterified product, ethyl acetate, from the reaction of 2 with p-NPA in the presence of ethanol. The pK(a) value of the ligated water molecule in 3 was estimated to be 10.7 by kinetic measurements in 40% MeCN aqueous solution at 25°C, I = 0.3.

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