Diacetoneglucose Complexes of Manganese(II) and Iron(II) and Their Organometallic Derivatization
详细信息 查看全文
- 作者：Umberto Piarulli ; Carlo Floriani ; Nazzareno Re ; Giuliana Gervasio ; and Davide Viterbo
- 刊名：Inorganic Chemistry
- 出版年：1998
- 出版时间：October 5, 1998
- 年：1998
- 卷：37
- 期：20
- 页码：5142 - 5148
- 全文大小：123K
- 年卷期：v.37,no.20(October 5, 1998)
- ISSN：1520-510X
文摘
Homoleptic metal-sugar complexes were obtained in the form of MnII- and FeII-diacetoneglucose derivatives.The protolysis of [Mn3Mes6] and [Fe2Mes4] (Mes = 2,4,6-Me3C6H2) with DAGH (1,2:5,6-di-O-isopropylidene-
-D-glucofuranose, diacetoneglucose) led to [M(DAG)2] [M = Mn (1), Fe (2)]. Although monomeric in solution,they showed a different degree of aggregation in the solid state, iron being monomeric and manganese oligomeric(see magnetic properties). Dimeric complexes from 1 and 2 were obtained in the reaction with 9,10-phenanthroline[phen], leading to [(phen)2M(
-DAG)2M(DAG)2] [M = Mn (3), Fe (4)]. The organometallic functionalizationof 1 and 2 was achieved via a ligand redistribution reaction mixing them with [Mn3Mes6] and [Fe2Mes4],respectively. The reaction led to mixed alkoxo aryl trinuclear complexes in the form of [(Mes)2M2(-DAG)2M(-Mes)2] [M = Mn (5), Fe (6)]. Both have a linear trimetallic skeleton with Mn···Mn and Fe···Fe averagedistances of 2.93 and 2.88 Å, respectively. The crystal data are as follows: complex 5, C60H82Mn3O12, monoclinic,space group P21, a = 10.289(5) Å, b = 20.878(5) Å, c = 14.015(5) Å, 
= 93.19(2)
, Z = 2; complex 6,C60H82Fe3O12, monoclinic, space group P21, a = 9.748(12) Å, b = 26.05(3) Å, c = 12.50(2) Å, = 107.50(2),Z = 2. The data were collected at -123 C. For 5 and 6 the magnetic analysis showed a strong antiferromagneticcoupling between the M(II) centers, with spin frustration leading to an overall S = 5/2 and S = 2 ground state,respectively.
-D-glucofuranose, diacetoneglucose) led to [M(DAG)2] [M = Mn (1), Fe (2)]. Although monomeric in solution,they showed a different degree of aggregation in the solid state, iron being monomeric and manganese oligomeric(see magnetic properties). Dimeric complexes from 1 and 2 were obtained in the reaction with 9,10-phenanthroline[phen], leading to [(phen)2M(-DAG)2M(DAG)2] [M = Mn (3), Fe (4)]. The organometallic functionalizationof 1 and 2 was achieved via a ligand redistribution reaction mixing them with [Mn3Mes6] and [Fe2Mes4],respectively. The reaction led to mixed alkoxo aryl trinuclear complexes in the form of [(Mes)2M2(-DAG)2M(-Mes)2] [M = Mn (5), Fe (6)]. Both have a linear trimetallic skeleton with Mn···Mn and Fe···Fe averagedistances of 2.93 and 2.88 Å, respectively. The crystal data are as follows: complex 5, C60H82Mn3O12, monoclinic,space group P21, a = 10.289(5) Å, b = 20.878(5) Å, c = 14.015(5) Å, = 93.19(2), Z = 2; complex 6,C60H82Fe3O12, monoclinic, space group P21, a = 9.748(12) Å, b = 26.05(3) Å, c = 12.50(2) Å, = 107.50(2),Z = 2. The data were collected at -123 C. For 5 and 6 the magnetic analysis showed a strong antiferromagneticcoupling between the M(II) centers, with spin frustration leading to an overall S = 5/2 and S = 2 ground state,respectively.