Formation, Structures, and Magnetic and EPR Spectroscopic Properties of Dicobalt(III)-Dicopper(II) Complexes Featuring Heterotetranuclear Cations of a Puckered Cyclic Structure with Diethanolamine and Diethanolamine(2−) as Bridging Ligands
✍ Scribed by Valeriya G. Makhankova; Olga Yu. Vassilyeva; Volodymyr N. Kokozay; Jan Reedijk; Gerard A. van Albada; Julia Jezierska; Brian W. Skelton
- Publisher
- John Wiley and Sons
- Year
- 2002
- Tongue
- English
- Weight
- 148 KB
- Volume
- 2002
- Category
- Article
- ISSN
- 1434-1948
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✦ Synopsis
The compounds [Cu II 2 Co III 2 (H 2 dea) 2 (dea) 4 ]X 2 (Solv) n [X = Cl (1), Br (2), SCN (3), O 2 CMe (4), I ( 5); Solv = H 2 O or/and CH 3 OH, DMF, n = 1-4] were synthesised by the reaction of zero-valent copper with cobalt(II) salts in non-aqueous (CH 3 OH, DMF, DMSO) solutions of diethanolamine (H 2 dea) in air. Crystallographic investigations of 1-4 reveal that the complexes contain the centrosymmetric cation [Cu 2 Co 2 (H 2 dea) 2 (dea) 4 ] 2+ in which the four metal atoms are linked together by bridging oxygen atoms of the six ligand groups to form a parallelogram with the length of the short edge (Cu•••Co) being ca. 2.83 A ˚and a short diagonal distance (Cu•••Cu) at approximately 3.23-3.29 A ˚. The copper atom is five-coordinate with a square-pyramidal geometry; the geometry at the trivalent cobalt ion is almost octahedral. The tetranuclear units are further stabilized by intramolecular O-H•••O and N-H•••O hydrogen bonds. The hydrogen-bon-
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