An investigation of Cu(II) and Ni(II)-catalysed hydrolysis of (di)imines
(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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https://lup.lub.lu.se/record/1727138
- author
- Czaun, Miklos LU ; Nelana, Simphiwe M. ; Guzei, Ilia A. ; Hasselgren, Catrin ; Hakansson, Mikael ; Jagner, Susan ; Lisensky, George ; Darkwa, James and Nordlander, Ebbe LU
- organization
- publishing date
- 2010
- 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
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060), Department of Chemistry (011001220)
- id
- 2f89ee40-725f-4e5a-95ef-81e77da6541a (old id 1727138)
- date added to LUP
- 2016-04-01 15:00:42
- date last changed
- 2022-01-28 03:37:36
@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}}, keywords = {{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}}, doi = {{10.1016/j.ica.2010.05.025}}, volume = {{363}}, year = {{2010}}, }