Binuclear Copper(II) Oxidation Products from Copper(I) Complexes with Tridentate Ligands. Magnetostructural Characterization
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- 作者：Darí ; o Rojas ; Ana M. Garcí ; a ; André ; s Vega ; Yanko Moreno ; Diego Venegas-Yazigi ; Marí ; a T. Garland ; and Jorge Manzur
- 刊名：Inorganic Chemistry
- 出版年：2004
- 出版时间：October 4, 2004
- 年：2004
- 卷：43
- 期：20
- 页码：6324 - 6330
- 全文大小：146K
- 年卷期：v.43,no.20(October 4, 2004)
- ISSN：1520-510X
文摘
The bis-pyridine tridentate ligands (6-R-2-pyridylmethyl)-(2-pyridylmethyl) benzylamine (RDPMA, where R = CH3,CF3), (6-R-2-pyridylmethyl)-(2-pyridylethyl) benzylamine (RPMPEA, where R = CH3, CF3), and the bidentate liganddi-benzyl-(6-methyl-2-pyridylmethyl)amine (BiBzMePMA) have been synthesized and their copper(I) complexesoxidized in a methanol solution to afford self-assembled bis-
-methoxo-binuclear copper(II) complexes (1, 2, 4, 6)or hydroxo- binuclear copper(II) complexes (3). Oxidation of the nonsubstituted DPMA (R = H) in dichloromethanegives a chloride-bridged complex (5). The crystal structures for [Cu(MeDPMA)(MeO)]2(ClO4)2 (1), [Cu(RPMPEA)(MeO)]2(ClO4)2 (for 2, R= Me, and for 4, R = CF3), [Cu(BiBzMePMA)(MeO)]2(ClO4)2 (6), [Cu(FDPMA)(OH)]2(ClO4)2 (3), and [Cu(DPMA)(Cl)]2(ClO4)2 (5) have been determined, and their variable-temperature magneticsusceptibility has been measured in the temperature range of 10-300 K. The copper coordination geometries arebest described as square pyramidal, except for 6, which is square planar, because of the lack of one pyridine ringin the bidentate ligand. In 1-4 and 6, the basal plane is formed by two pyridine N atoms and two O atoms fromthe bridging methoxo or hydroxo groups, whereas in 5, the bridging Cl atoms occupy axial-equatorial sites. Magneticsusceptibility measurements show that the Cu atoms are strongly coupled antiferromagnetically in the bis-methoxocomplexes 1, 2, 4, and 6, with -2J > 600 cm-1, whereas for the hydroxo complex 3, -2J = 195 cm-1 and thechloride-bridged complex 5 shows a weak ferromagnetic coupling, with 2J = 21 cm-1 (2J is an indicator of themagnetic interaction between the Cu centers).
-methoxo-binuclear copper(II) complexes (1, 2, 4, 6)or hydroxo- binuclear copper(II) complexes (3). Oxidation of the nonsubstituted DPMA (R = H) in dichloromethanegives a chloride-bridged complex (5). The crystal structures for [Cu(MeDPMA)(MeO)]2(ClO4)2 (1), [Cu(RPMPEA)(MeO)]2(ClO4)2 (for 2, R= Me, and for 4, R = CF3), [Cu(BiBzMePMA)(MeO)]2(ClO4)2 (6), [Cu(FDPMA)(OH)]2(ClO4)2 (3), and [Cu(DPMA)(Cl)]2(ClO4)2 (5) have been determined, and their variable-temperature magneticsusceptibility has been measured in the temperature range of 10-300 K. The copper coordination geometries arebest described as square pyramidal, except for 6, which is square planar, because of the lack of one pyridine ringin the bidentate ligand. In 1-4 and 6, the basal plane is formed by two pyridine N atoms and two O atoms fromthe bridging methoxo or hydroxo groups, whereas in 5, the bridging Cl atoms occupy axial-equatorial sites. Magneticsusceptibility measurements show that the Cu atoms are strongly coupled antiferromagnetically in the bis-methoxocomplexes 1, 2, 4, and 6, with -2J > 600 cm-1, whereas for the hydroxo complex 3, -2J = 195 cm-1 and thechloride-bridged complex 5 shows a weak ferromagnetic coupling, with 2J = 21 cm-1 (2J is an indicator of themagnetic interaction between the Cu centers).