Synthesis, Structure, and Magnetic Properties of Transition Metal Complexes of the Nitroxide 2,5-Dihydro-4,5,5-trimethyl-2,2-bis(2-pyridyl)imidazole-1-oxyl.
With the radical 2,5-dihydro-4,5,5-trimethyl-2,2-bis(2-pyridyl)imidazole-1-oxyl (L) a series of transition metal complexes have been prepared: [ML(2)](SbF(6))(2) with M(2+) = Mn(2+) (1), Fe(2+) (2), Co(2+) (3), Ni(2+) (4), Cu(2+) (5), and Zn(2+) (6), Cu(L)(Cl)(2)(MeOH) (7), and Cu(L)SO(4).H(2)O (8). The structures of 1, 3, and 6 were determined by X-ray structural analyses. In these compounds the tridendate L is coordinated to the metal ion by the two pyridine nitrogen donors and by the oxygen atom of the nitroxide group. The N-O bond distances are 1.25(2) Å (1), 1.267(13) Å (3), and 1.260(11) Å (6). The M-O-N angles are 117.0(10) degrees (1), 114.5(8) degrees (3), and 114.2(7) degrees (6). Crystal data: space group P2(1)/n, for 1, 3, and 6; compound 1, a = 10.806(3) Å, b = 14.101(6) Å, c = 14.253(4) Å, beta = 108.82(2) degrees, V = 2055.7(12) Å(3), Z = 2, R(1) = 0.0677, wR(2) = 0.1512. Compound 3, a = 10.761(4) Å, b = 14.253(6) Å, c = 14.108(5) Å, beta = 111.16(3) degrees, V = 2017.9(13) Å(3), Z = 2, R(1) = 0.0702, wR(2) = 0.1460; compound 6, a = 10.788(2) Å, b = 14.147(3) Å, c = 14.196(3) Å, beta = 109.93(3) degrees, V = 2036.8(7) Å(3), Z = 2, R(1) = 0.0573, wR(2) = 0.1194. Magnetic measurements of 1, 2, 5, and 8 show strong antiferromagnetic interaction between the spin of the metal ion and the spin of the radical which increases at lower temperatures. For 6 the magnetic moment corresponds to two noninteracting spins in the temperature range 60-300 K.
Hintermaier
Frank
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Institut für Anorganische Chemie, Ludwig-Maximilians-Universität, Meiserstrasse 1, D-80333 Munich, Germany, and Institute of Organic Chemistry, Russian Academy of Sciences, Prospect Lavren'teva, 630090 Novosibirsk, Russia.
Sünkel
Karlheinz
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Volodarsky
Leonid B.
LB
Beck
Wolfgang
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