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Breeze SR, Wang S, Greedan JE, Raju NP: Copper and Bismuth Complexes Containing Dipyridyl gem-Diolato Ligands: Bi (III)(2)[(2-Py)(2) CO (OH)](2)(O (2) CCF (3))(4)(THF)(2), Cu (II)[(2-Py)(2) CO (OH)](2)(HO (2) CCH (3))(2), and Cu (II)(4)[(2-Py)(2) CO (OH)](2)(O (2) CCH (3))(6)(H (2) O)(2), a Ferromagnetically Coupled Tetranuclear Copper (II) Chain. Inorg Chem. 1996 Nov 20;35(24):6944-6951.
The reactions of the singly deprotonated di-2-pyridylmethanediol ligand (dpmdH (-)) with copper (II) and bismuth (III) have been investigated. A new dinuclear bismuth (III) complex Bi (2)(dpmdH)(2)(O (2) CCF (3))(4)(THF)(2), 1, has been obtained by the reaction of BiPh (3) with di-2-pyridyl ketone in the presence of HO (2) CCF (3) in tetrahydrofuran (THF). The reaction of Cu (OCH (3))(2) with di-2-pyridyl ketone, H (2) O, and acetic acid in a 1:2:2:2 ratio yielded a mononuclear complex Cu [(2-Py)(2) CO (OH)](2)(HO (2) CCH (3))(2), 2, while the reaction of Cu (OAC)(2)(H (2) O) with di-2-pyridyl ketone and acetic acid in a 2:1:1 ratio yielded a tetranuclear complex Cu (4)[(2-Py)(2) CO (OH)](2)(O (2) CCH (3))(6)(H (2) O)(2), 3. The structures of these complexes were determined by single-crystal X-ray diffraction analyses. Three different bonding modes of the dpmdH (-) ligand were observed in compounds 1-3. In 2, the dpmdH (-) ligand functions as a tridentate chelate to the copper center and forms a hydrogen bond between the OH group and the noncoordinating HO (2) CCH (3) molecule. In 1 and 3, the dpmdH (-) ligand functions as a bridging ligand to two metal centers through the oxygen atom. The two pyridyl groups of the dpmdH (-) ligand are bound to one bismuth (III) center in 1, while in 3 they are bound two copper (II) centers, respectively. Compound 3 has an unusual one dimensional hydrogen bonded extended structure. The intramolecular magnetic interaction in 3 has been found to be dominated by ferromagnetism. Crystal data: 1, C (38) H (34) N (4) O (14) F (12) Bi (2), triclinic P&onemacr;, a = 11.764 (3) A, b = 11.949 (3) A, c = 9.737 (1) A, alpha =101.36 (2) degrees, beta = 105.64 (2) degrees, gamma = 63.79 (2) degrees, Z = 1; 2, C (26) H (26) N (4) O (8) Cu/CH (2) Cl (2), monoclinic C2/c, a = 25.51 (3) A, b = 7.861 (7) A, c = 16.24 (2) A, beta = 113.08 (9) degrees, Z = 4; 3, C (34) H (40) N (4) O (18) Cu (4)/CH (2) Cl (2), triclinic P&onemacr;, a = 10.494 (2) A, b = 13.885 (2) A, c = 7.900 (4) A, alpha =106.52 (2) degrees, beta = 90.85 (3) degrees, gamma = 94.12 (1) degrees, Z = 1. |
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