Synthesis and Characterization of a Series of Edge-Sharing Octahedral-Tetrahedral-Octahedral Linear Trinuclear Complexes [M3(L1O)4]2+, Where M = Mn2+, Co
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- 作者：Timothy C. Higgs ; K. Spartalian ; Charles J. O'Connor ; Berthold F. Matzanke ; and Carl J. Carrano
- 刊名：Inorganic Chemistry
- 出版年：1998
- 出版时间：May 4, 1998
- 年：1998
- 卷：37
- 期：9
- 页码：2263 - 2272
- 全文大小：132K
- 年卷期：v.37,no.9(May 4, 1998)
- ISSN：1520-510X
文摘
The mixed functionality pyrazole/phenol ligand(2-hydroxyphenyl)bis(pyrazolyl)methane, L1OH, has beenusedto prepare a series of linear trimetallic systems with the generalstructural motif[M3(L1O)4]2+, where M =Mn2+,Co2+, Ni2+, Cu2+, andZn2+. Each of these complexes has been structurallycharacterized by X-ray crystallographygiving the following structural parameters:[Zn3(L1O)4][BF4]2·H2O,C52H44N16B2F8O5Zn3,monoclinic, a =18.572(4) Å, b = 22.400(5) Å, c= 15.921(3), 
fchars/beta2.gif" BORDER=0 ALIGN="middle"> = 112.439(8)
f">, space groupC2/c, Z = 4;[Cu3(L1O)4][BF4]2·2MeCN,C56H44N18B2Cu3F8O4,monoclinic, a = 40.574(2) Å, b =16.701(1) Å, c = 19.841(2) Å, fchars/beta2.gif" BORDER=0 ALIGN="middle">=111.388(5)f">, space group C2/c,Z = 8;[Ni3(L1O)4][ClO4]2·MeCN·0.5H2O,C54H44N17Cl2Ni3O12.5,monoclinic, a= 12.324(4) Å, b = 26.537(2) Å, c= 18.829(3) Å, fchars/beta2.gif" BORDER=0 ALIGN="middle"> = 102.78(1)f">, space groupC2/c, Z = 4;[Co3(L1O)4][BF4]2·MeCN,C54H44N17B2Co3F8O4,monoclinic, a = 12.395(2) Å, b =26.483(3) Å, c = 18.703(4) Å, fchars/beta2.gif" BORDER=0 ALIGN="middle">=103.22(2)f">, space group C2/c, Z= 4;[Mn3(L1O)4(MeCN)][ClO4]2·1.4MeCN,C56.68H44N18.34Cl2Mn3O12,orthorhombic, a = 15.471(2) Å, b =17.364(2) Å, c = 24.216(2) Å, space groupPbcn, Z = 4. For Zn2+,Cu2+, Ni2+,and Co2+ the central metal atom of the linear trimetallic[M3(L1O)4]2+ unit is fourcoordinate and has apseudotetrahedral geometry with a dihedral angle, fchars/omega.gif" BORDER=0 >, between the twoMcentralO2Mterminal planes of79.9f"> (Zn),61.2f"> (Co), 60.4f"> (Ni), and 46.8f"> (Cu). The centralMn2+ atom of[Mn3(L1O)4(MeCN)][ClO4]2·1.4MeCNisfive-coordinate, with a trigonal bipyramidal stereochemistry, theresult of an equatorially coordinated MeCNsolvent molecule. Variable-temperature magnetic data indicate thatthe Ni, Cu, and Mn complexes display modestantiferromagnetic coupling between the metal centers, while the Coderivative is strongly ferromagnetically coupled.
fchars/beta2.gif" BORDER=0 ALIGN="middle"> = 112.439(8)f">, space groupC2/c, Z = 4;[Cu3(L1O)4][BF4]2·2MeCN,C56H44N18B2Cu3F8O4,monoclinic, a = 40.574(2) Å, b =16.701(1) Å, c = 19.841(2) Å, fchars/beta2.gif" BORDER=0 ALIGN="middle">=111.388(5)f">, space group C2/c,Z = 8;[Ni3(L1O)4][ClO4]2·MeCN·0.5H2O,C54H44N17Cl2Ni3O12.5,monoclinic, a= 12.324(4) Å, b = 26.537(2) Å, c= 18.829(3) Å, fchars/beta2.gif" BORDER=0 ALIGN="middle"> = 102.78(1)f">, space groupC2/c, Z = 4;[Co3(L1O)4][BF4]2·MeCN,C54H44N17B2Co3F8O4,monoclinic, a = 12.395(2) Å, b =26.483(3) Å, c = 18.703(4) Å, fchars/beta2.gif" BORDER=0 ALIGN="middle">=103.22(2)f">, space group C2/c, Z= 4;[Mn3(L1O)4(MeCN)][ClO4]2·1.4MeCN,C56.68H44N18.34Cl2Mn3O12,orthorhombic, a = 15.471(2) Å, b =17.364(2) Å, c = 24.216(2) Å, space groupPbcn, Z = 4. For Zn2+,Cu2+, Ni2+,and Co2+ the central metal atom of the linear trimetallic[M3(L1O)4]2+ unit is fourcoordinate and has apseudotetrahedral geometry with a dihedral angle, fchars/omega.gif" BORDER=0 >, between the twoMcentralO2Mterminal planes of79.9f"> (Zn),61.2f"> (Co), 60.4f"> (Ni), and 46.8f"> (Cu). The centralMn2+ atom of[Mn3(L1O)4(MeCN)][ClO4]2·1.4MeCNisfive-coordinate, with a trigonal bipyramidal stereochemistry, theresult of an equatorially coordinated MeCNsolvent molecule. Variable-temperature magnetic data indicate thatthe Ni, Cu, and Mn complexes display modestantiferromagnetic coupling between the metal centers, while the Coderivative is strongly ferromagnetically coupled.