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An investigation of Cu(II) and Ni(II)-catalysed hydrolysis of (di)imines

Czaun, Miklos LU ; Nelana, Simphiwe M.; Guzei, Ilia A.; Hasselgren, Catrin; Hakansson, Mikael; Jagner, Susan; Lisensky, George; Darkwa, James and Nordlander, Ebbe LU (2010) In Inorganica Chimica Acta 363(12). p.3102-3112
Abstract
The reactions of six diimine ligands with Cu(II) and Ni(II) halide salts have been investigated. The diimine ligands were Ph2C=N(CH2)(n)NC=Ph-2 (n = 2 (Bz(2)en, 1a), 3 (Bz(2)pn, 1b), 4 (Bz2bn, 1c)), N, N'-bis-(2-tert-butylthio- 1-ylmethylenebenzene)-2,2'diamino-biphenyl (2), N,N'-bis-(2-chloro-1-ylmethylenebenzene)-1,3diaminobenzene (3) and N,N'-bis-(2-chloro-1-ylmethylenebenzene)-1,2-ethanediamine (4). Reactions of 1a-c, 2-4 with CuCl2 center dot 2H(2)O in dry ethanol at ambient temperature led to complete or partial hydrolysis of the diimine ligands to ultimately form copper diamine complexes. The non-hydrolyzed complexes of 1b and 1c, [Cu(L)Cl-2] (L = 1b, 1c), could be isolated when the reactions were carried out at low temperatures,... (More)
The reactions of six diimine ligands with Cu(II) and Ni(II) halide salts have been investigated. The diimine ligands were Ph2C=N(CH2)(n)NC=Ph-2 (n = 2 (Bz(2)en, 1a), 3 (Bz(2)pn, 1b), 4 (Bz2bn, 1c)), N, N'-bis-(2-tert-butylthio- 1-ylmethylenebenzene)-2,2'diamino-biphenyl (2), N,N'-bis-(2-chloro-1-ylmethylenebenzene)-1,3diaminobenzene (3) and N,N'-bis-(2-chloro-1-ylmethylenebenzene)-1,2-ethanediamine (4). Reactions of 1a-c, 2-4 with CuCl2 center dot 2H(2)O in dry ethanol at ambient temperature led to complete or partial hydrolysis of the diimine ligands to ultimately form copper diamine complexes. The non-hydrolyzed complexes of 1b and 1c, [Cu(L)Cl-2] (L = 1b, 1c), could be isolated when the reactions were carried out at low temperatures, and the half-hydrolyzed complex [Cu(Bzpn)Cl-2] could also be identified via X-ray crystallography. Similarly, reactions of 1a or 1b with NiCl2 center dot 6H(2)O or [NiBr2(dme)] led to rapid hydrolysis of the imines and Ni complexes containing half-hydrolyzed 1a (Bzen; [trans-[Ni(Bzen)(2)Br-2]) and 1b (Bzpn; [Ni(Bzpn) Br-2] could be isolated and identified via single crystal X-ray analysis. Kinetic studies were made of the hydrolyses of 1a, 1b in THF and 2 in acetone, in the presence of Cu(II), and of 1a in acetonitrile, in the presence of Ni(II). Activation parameters were determined for the latter reaction and for the copper-catalyzed hydrolysis of 2; the relatively large negative activation entropies clearly indicate rate-determining steps of an associative nature. (C) 2010 Elsevier B.V. All rights reserved. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Nickel, Copper, Catalysis, Diimine, Hydrolysis
in
Inorganica Chimica Acta
volume
363
issue
12
pages
3102 - 3112
publisher
Elsevier
external identifiers
  • wos:000282360200055
  • scopus:77957316188
ISSN
0020-1693
DOI
10.1016/j.ica.2010.05.025
language
English
LU publication?
yes
id
2f89ee40-725f-4e5a-95ef-81e77da6541a (old id 1727138)
date added to LUP
2010-11-26 14:49:29
date last changed
2018-05-29 11:27:12
@article{2f89ee40-725f-4e5a-95ef-81e77da6541a,
  abstract     = {The reactions of six diimine ligands with Cu(II) and Ni(II) halide salts have been investigated. The diimine ligands were Ph2C=N(CH2)(n)NC=Ph-2 (n = 2 (Bz(2)en, 1a), 3 (Bz(2)pn, 1b), 4 (Bz2bn, 1c)), N, N'-bis-(2-tert-butylthio- 1-ylmethylenebenzene)-2,2'diamino-biphenyl (2), N,N'-bis-(2-chloro-1-ylmethylenebenzene)-1,3diaminobenzene (3) and N,N'-bis-(2-chloro-1-ylmethylenebenzene)-1,2-ethanediamine (4). Reactions of 1a-c, 2-4 with CuCl2 center dot 2H(2)O in dry ethanol at ambient temperature led to complete or partial hydrolysis of the diimine ligands to ultimately form copper diamine complexes. The non-hydrolyzed complexes of 1b and 1c, [Cu(L)Cl-2] (L = 1b, 1c), could be isolated when the reactions were carried out at low temperatures, and the half-hydrolyzed complex [Cu(Bzpn)Cl-2] could also be identified via X-ray crystallography. Similarly, reactions of 1a or 1b with NiCl2 center dot 6H(2)O or [NiBr2(dme)] led to rapid hydrolysis of the imines and Ni complexes containing half-hydrolyzed 1a (Bzen; [trans-[Ni(Bzen)(2)Br-2]) and 1b (Bzpn; [Ni(Bzpn) Br-2] could be isolated and identified via single crystal X-ray analysis. Kinetic studies were made of the hydrolyses of 1a, 1b in THF and 2 in acetone, in the presence of Cu(II), and of 1a in acetonitrile, in the presence of Ni(II). Activation parameters were determined for the latter reaction and for the copper-catalyzed hydrolysis of 2; the relatively large negative activation entropies clearly indicate rate-determining steps of an associative nature. (C) 2010 Elsevier B.V. All rights reserved.},
  author       = {Czaun, Miklos and Nelana, Simphiwe M. and Guzei, Ilia A. and Hasselgren, Catrin and Hakansson, Mikael and Jagner, Susan and Lisensky, George and Darkwa, James and Nordlander, Ebbe},
  issn         = {0020-1693},
  keyword      = {Nickel,Copper,Catalysis,Diimine,Hydrolysis},
  language     = {eng},
  number       = {12},
  pages        = {3102--3112},
  publisher    = {Elsevier},
  series       = {Inorganica Chimica Acta},
  title        = {An investigation of Cu(II) and Ni(II)-catalysed hydrolysis of (di)imines},
  url          = {http://dx.doi.org/10.1016/j.ica.2010.05.025},
  volume       = {363},
  year         = {2010},
}