Mono- and dinuclear transition metal complexes of the hexadentate ligand tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane (L)

Beissel T, Glaser T, Kesting F, Wieghardt K, Nuber B (1996)
Inorganic Chemistry 35(13): 3936-3947.

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Abstract / Bemerkung
The hexadentate, pendant arm macrocycle 1,4,7-tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacylononane (H(3)L) has been synthesized and isolated as its trihydrochloride, H(3)L . 3HCl, or sodium salt, Na(3)L, and its coordination chemistry with first-row transition metals has been studied. Mononuclear complexes of the type [LM(III)] (M Ga (1), In (2), V (3), Cr (4), Mn (5), Fe,Co (6)) have been isolated as have the one-electron-oxidized forms [LM]PF6 (M = V-IV (3a), Mn-IV (5a)). The crystal structure of 6 has been determined by single-crystal X-ray crystallography. Complex 6 crystallizes in the orthorhombic space group Iba2, with cell constants a = 14.206(8) Angstrom, b = 22.53(1) Angstrom, c = 26.07(1) Angstrom, V = 8344.0(3) Angstrom(3), and Z = 8. The cobalt(III) ion is in a distorted octahedral fac-N3S3 donor set. The reaction of L with divalent metal chlorides in a 1:2 ratio in methanol affords the homodinuclear complexes [LM(2)(II)Cl] (M = Mn (7), Co (8), Ni (9), Zn (10), Cd (11)) where one metal is six(N(3)MS(3)) and the other is four-coordinate (S(3)MCl); the two polyhedra are linked by three Lcp-thiolato bridges. Heterodinuclear complexes of the type [LM(1)M(2)Cl] have been obtained from [LM(2)Cl] species by abstraction of the four-coordinate metal ion and replacement by a different metal ion. The complexes [LZn(II)M(II)Cl] (M = Fe (12), Co (13), Ni (14)), [LNi(II)M(II)Cl] (M = Co (15), Zn (16)), and [LMn(II)M(II)Cl] (M = Fe (17), Co (18), Ni (19), Zn (20), Cd (21), Hg (22)) have been isolated as solid materials. The crystal structure of 14 has been determined by X-ray crystallography. Complex 14 crystallizes in the orthorhombic space group P2(1)2(1)2(1), with cell constants a = 15.45(1) Angstrom, b = 17.77(1) Angstrom, c = 17.58(1) Angstrom, V = 4826.5(4) Angstrom(3), and Z = 4. The linkage isomers 14 and 16 show characteristic electronic spectra for octahedrally and tetrahedrally coordinated Ni(II), respectively. The electronic structures of new complexes have been investigated by UV-vis spectroscopy; their magnetochemistry and electrochemistry are reported.
Erscheinungsjahr
Zeitschriftentitel
Inorganic Chemistry
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35
Zeitschriftennummer
13
Seite
3936-3947
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Beissel T, Glaser T, Kesting F, Wieghardt K, Nuber B. Mono- and dinuclear transition metal complexes of the hexadentate ligand tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane (L). Inorganic Chemistry. 1996;35(13):3936-3947.
Beissel, T., Glaser, T., Kesting, F., Wieghardt, K., & Nuber, B. (1996). Mono- and dinuclear transition metal complexes of the hexadentate ligand tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane (L). Inorganic Chemistry, 35(13), 3936-3947. doi:10.1021/ic951623u
Beissel, T., Glaser, T., Kesting, F., Wieghardt, K., and Nuber, B. (1996). Mono- and dinuclear transition metal complexes of the hexadentate ligand tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane (L). Inorganic Chemistry 35, 3936-3947.
Beissel, T., et al., 1996. Mono- and dinuclear transition metal complexes of the hexadentate ligand tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane (L). Inorganic Chemistry, 35(13), p 3936-3947.
T. Beissel, et al., “Mono- and dinuclear transition metal complexes of the hexadentate ligand tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane (L)”, Inorganic Chemistry, vol. 35, 1996, pp. 3936-3947.
Beissel, T., Glaser, T., Kesting, F., Wieghardt, K., Nuber, B.: Mono- and dinuclear transition metal complexes of the hexadentate ligand tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane (L). Inorganic Chemistry. 35, 3936-3947 (1996).
Beissel, T, Glaser, Thorsten, Kesting, F, Wieghardt, K, and Nuber, B. “Mono- and dinuclear transition metal complexes of the hexadentate ligand tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane (L)”. Inorganic Chemistry 35.13 (1996): 3936-3947.

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