Mono- and Dinuclear Transition Metal Complexes of the Hexadentate Ligand Tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane (L)
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- 作者：Thomas Beissel ; Thorsten Glaser ; Frank Kesting ; Karl Wieghardt ; and Bernhard Nuber
- 刊名：Inorganic Chemistry
- 出版年：1996
- 出版时间：June 19, 1996
- 年：1996
- 卷：35
- 期：13
- 页码：3936 - 3947
- 全文大小：520K
- 年卷期：v.35,no.13(June 19, 1996)
- ISSN：1520-510X
文摘
The hexadentate, pendant arm macrocycle1,4,7-tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane(H3L)has been synthesized and isolated as its trihydrochloride,H3L·3HCl, or sodium salt, Na3L, and itscoordinationchemistry with first-row transition metals has been studied.Mononuclear complexes of the type [LMIII] (M=Ga (1), In (2), V (3), Cr(4), Mn (5), Fe,Co (6)) have beenisolated as have the one-electron-oxidized forms[LM]PF6 (M = VIV (3a),MnIV (5a)). The crystal structure of6 has been determined by single-crystal X-raycrystallography. Complex 6 crystallizes in theorthorhombic space group Iba2, with cell constantsa = 14.206(8)Å, b = 22.53(1) Å, c = 26.07(1)Å, V = 8344.0(3) Å3, and Z= 8. The cobalt(III) ion is in a distortedoctahedralfac-N3S3 donor set. Thereaction of L with divalent metal chlorides in a 1:2 ratio in methanolaffords thehomodinuclear complexes [LMII2Cl] (M =Mn (7), Co (8), Ni (9), Zn(10), Cd (11)) where one metal issix-(N3MS3) and the other is four-coordinate(S3MCl); the two polyhedra are linked by three
2-thiolato bridges.Heterodinuclear complexes of the type[LM1M2Cl] have been obtained from[LM2Cl] species by abstraction ofthe four-coordinate metal ion and replacement by a different metal ion.The complexes [LZnIIMIICl] (M= Fe(12), Co (13), Ni (14)),[LNiIIMIICl] (M = Co (15),Zn (16)), and [LMnIIMIICl] (M= Fe (17), Co (18), Ni(19),Zn (20), Cd (21), Hg (22)) have beenisolated as solid materials. The crystal structure of14 has been determinedby X-ray crystallography. Complex 14 crystallizes inthe orthorhombic space groupP212121, with cellconstantsa = 15.45(1) Å, b = 17.77(1) Å,c = 17.58(1) Å, V = 4826.5(4)Å3, and Z = 4. The linkage isomers14 and 16show characteristic electronic spectra for octahedrally andtetrahedrally coordinated Ni(II), respectively.Theelectronic structures of new complexes have been investigated byUV-vis spectroscopy; their magnetochemistryand electrochemistry are reported.
2-thiolato bridges.Heterodinuclear complexes of the type[LM1M2Cl] have been obtained from[LM2Cl] species by abstraction ofthe four-coordinate metal ion and replacement by a different metal ion.The complexes [LZnIIMIICl] (M= Fe(12), Co (13), Ni (14)),[LNiIIMIICl] (M = Co (15),Zn (16)), and [LMnIIMIICl] (M= Fe (17), Co (18), Ni(19),Zn (20), Cd (21), Hg (22)) have beenisolated as solid materials. The crystal structure of14 has been determinedby X-ray crystallography. Complex 14 crystallizes inthe orthorhombic space groupP212121, with cellconstantsa = 15.45(1) Å, b = 17.77(1) Å,c = 17.58(1) Å, V = 4826.5(4)Å3, and Z = 4. The linkage isomers14 and 16show characteristic electronic spectra for octahedrally andtetrahedrally coordinated Ni(II), respectively.Theelectronic structures of new complexes have been investigated byUV-vis spectroscopy; their magnetochemistryand electrochemistry are reported.