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Synthesis and Structural Characterization of Trinuclear CuII−Pyrazolato Complexes Containing μ3-OH, μ3-O, and μ3-Cl Ligands. Magnetic Susceptibility Study of [PPN]2[(μ3-O)Cu3(μ-pz)3Cl3]
Abstract
The nine-membered [-Cu(II)-N-N-](3) ring of trimeric copper-pyrazolato complexes provides a sturdy framework on which water is twice deprotonated in consecutive steps, forming mu(3)-OH and mu(3)-O species. In the presence of excess chlorides the mu(3)-O(H) ligand is replaced by two mu(3)-Cl ions. The interconversion of mu(3)-OH and mu(3)-O and the exchange of mu(3)-O(H) and mu(3)-Cl are reversible, and the three species involved have been structurally characterized: [PPN][Cu(3)(mu(3)-OH)(mu-pz)(3)Cl(3)(thf)].CH(2)Cl(2) (1a), monoclinic P2(1)/n, a = 10.055(2) A, b = 35.428(5) A, c = 15.153(2) A, beta = 93.802(3) degrees, V = 5386(1) A(3), Z = 4; [Bu(4)N][Cu(3)(mu(3)-OH)(mu-pz)(3)Cl(3)] (1b), triclinic P-1, a = 9.135(2) A, b = 13.631(2) A, c = 14.510(2) A, alpha = 67.393(2) degrees, beta = 87.979(2) degrees, gamma = 80.268(3) degrees, V = 1643.2(4) A(3), Z = 2; [PPN](2)[Cu(3)(mu(3)-O)(mu-pz)(3)Cl(3)] (2), monoclinic P2/c, a = 12.807(2) A, b = 13.093(2) A, c = 23.139(4) A, beta = 105.391(3) degrees, V = 3741(1) A(3), Z = 2; [PPN](2)[Cu(3)(mu(3)-Cl)(2)(mu-pz)(3)Cl(3)].0.75H(2)O.0.5CH(2)Cl(2) (3a), triclinic P-1, a = 14.042(2) A, b = 23.978(4) A, c = 25.195(4) A, alpha = 76.796(3) degrees, beta = 79.506(3) degrees, gamma = 77.629(3) degrees, V = 7988(2) A(3), Z = 4; [Bu(4)N](2)[Cu(3)(mu(3)-Cl)(2)(mu-pz)(3)Cl(3)] (3b), monoclinic C2/c, a = 17.220(2) A, b = 15.606(2) A, c = 20.133(2) A, beta = 103.057(2) degrees, V = 5270(1) A(3), Z = 4; [Et(3)NH][Cu(3)(mu(3)-OH)(mu-pz)(3)Cl(3)(pzH)] (4), triclinic P-1, a = 11.498(2) A, b = 11.499(2) A, c = 12.186(2) A, alpha = 66.475(3) degrees, beta = 64.279(3) degrees, gamma = 80.183(3) degrees, V = 1331.0(5) A(3), Z = 2. Magnetic susceptibility measurements show that the three copper centers of 2 are strongly antiferromagnetically coupled with J(Cu-Cu) = -500 cm(-1).
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Cites
Multicopper oxidases and oxygenases
Solomon, E. I., Sundaram, U. M., & Machonkin, T. E. (1996) · Chemical Reviews · doi:10.1021/cr950046o · Cited by 3,664
Cited by
Trinuclear Metallacycles: Metallatriangles and Much More
Zangrando, E., Casanova, M., & Alessio, E. (2008) · Chemical Reviews · doi:10.1021/cr8002449 · Cited by 274
Metadata
- Authors
- Angaridis, P. A., Baran, P., Boča, R., Cervantes-Lee, F., Haase, W., Mezei, G., Raptis, R. G., & Werner, R.
- Venue
- Inorganic Chemistry
- Publisher
- American Chemical Society (ACS)
- Published
- 2002-03-26
- Volume
- 41
- Issue
- 8
- Pages
- 2219-2228
- ISSN
- 0020-1669 (ISSN-L)
- 1520-510X
- OpenAlex
- W1970437837
- Cited by
- 177
- References
- 1
- FWCI
- 6.70
- Type
- journal article
- Language
- en
- Open access
- closed
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- CoChat. (2026). Citation check: Synthesis and Structural Characterization of Trinuclear CuII−Pyrazolato Complexes Containing μ3-OH, μ3-O, and μ3-Cl Ligands. Magnetic Susceptibility Study of [PPN]2[(μ3-O)Cu3(μ-pz)3Cl3]. https://app.cochat.ai/papers/10.1021/ic010670l
- The paper
- Angaridis, P. A., Baran, P., Boča, R., Cervantes-Lee, F., Haase, W., Mezei, G., Raptis, R. G., & Werner, R. (2002). Synthesis and Structural Characterization of Trinuclear CuII−Pyrazolato Complexes Containing μ3-OH, μ3-O, and μ3-Cl Ligands. Magnetic Susceptibility Study of [PPN]2[(μ3-O)Cu3(μ-pz)3Cl3]. Inorganic Chemistry. https://doi.org/10.1021/ic010670l
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