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- Czaun, MiklosLund University,Lunds universitet,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH (author)
An investigation of Cu(II) and Ni(II)-catalysed hydrolysis of (di)imines
- Article/chapterEnglish2010
Publisher, publication year, extent ...
- Elsevier BV,2010
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- LIBRIS-ID:oai:research.chalmers.se:27e2b1f1-0a3d-4e2e-ba00-a14d0ed635bc
- https://doi.org/10.1016/j.ica.2010.05.025DOI
- https://research.chalmers.se/publication/128119URI
- https://lup.lub.lu.se/record/1727138URI
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- Language:English
- Summary in:English
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- 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.
Subject headings and genre
- NATURVETENSKAP Kemi hsv//swe
- NATURAL SCIENCES Chemical Sciences hsv//eng
- NATURVETENSKAP Fysik Atom- och molekylfysik och optik hsv//swe
- NATURAL SCIENCES Physical Sciences Atom and Molecular Physics and Optics hsv//eng
- Hydrolysis
- Catalysis
- molecular-structure
- copper(ii) complexes
- Copper
- Nickel
- ligands
- chromophores
- Diimine
- crystal
- Nickel
- Copper
- Catalysis
- Diimine
- Hydrolysis
Added entries (persons, corporate bodies, meetings, titles ...)
- Nelana, S. M.Vaal University of Technology,University of Johannesburg (author)
- Guzei, I. A.University of Wisconsin Madison (author)
- Hasselgren, Catrin,1970Chalmers tekniska högskola,Chalmers University of Technology(Swepub:cth)catrin (author)
- Hakansson, M.Göteborgs universitet,University of Gothenburg (author)
- Jagner, Susan Elisabeth,1940Chalmers tekniska högskola,Chalmers University of Technology(Swepub:cth)susan (author)
- Lisensky, G.Beloit College (author)
- Darkwa, J.University of Johannesburg (author)
- Nordlander, EbbeLund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH(Swepub:lu)ook1-eno (author)
- Kemiska institutionenInstitutioner vid LTH (creator_code:org_t)
Related titles
- In:Inorganica Chimica Acta: Elsevier BV363:12, s. 3102-31120020-1693
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