Preparation and properties of mononuclear and ferromagnetically coupled dinuclear manganese complexes with 2,2'-biphenoxide
Preparation and properties of mononuclear and ferromagnetically coupled dinuclear manganese complexes with 2,2'-biphenoxide
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DOI：
10.1021/ic00016a017
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发表时间：
1991-08
影响因子：
4.6
通讯作者：
A. Schake;Edward A. Schmitt;A. Conti;W. E. Streib;J. Huffman;D. Hendrickson;G. Christou
中科院分区：
文献类型：
--
作者：
A. Schake;Edward A. Schmitt;A. Conti;W. E. Streib;J. Huffman;D. Hendrickson;G. Christou
The treatment of Mn{sub 3}O(O{sub 2}CPh){sub 6}(py){sub 2}(H{sub 2}O) with 2,2{prime}-biphenol (biphenH{sub 2}) and NEt{sub 3} in MeCN leads to formation of (NEt{sub 3}H){sub 2}(Mn(biphen){sub 2}(biphenH)) (2), and the crystal structure is reported. A similar reaction system using 3,3{prime}, 5,5{prime}-tetra-bromobiphenol leads to the product (NEt{sub 3}H){sub 2}(Mn(Br{sub 4}biphen){sub 2}(O{sub 2}CPh)) (3) whose IR spectrum suggests its structure to be similar to 2 with a chelating ({eta}{sup 2}) benzoate replacing the monodentate biphenH group. Treatment of complex 2 with 2,2{prime}-bipyriding (bpy) in CH{sub 2}CI{sub 2} yields a black solution: layering with hexanes and storage at {minus}20C leads to crystallization of Mn{sub 2}(biphen){sub 2}(biphenH)(byp){sub 2} (4) whereas storage at room temperature leads to crystallization of (bpyH)(Mn(biphen){sub 2}(bpy)) (5) The crystal structure of complex 4 is reported. The complex is mixed-valence (Mn{sup II},Mn{sup III}), and the structure consists of two Mn atoms bridged by two oxygen atoms from two biphen groups, the other oxygen atoms of which are terminally ligated to the Mn{sup III} center. Six-coordination of the latter is completed by a chelating bpy. The Mn{sup II} has a chelating bpy, and five-coordination is completed by a monodentate biphenH, the second oxygen of which is protonated as in 2. The Mn{sup II}more » and Mn{sup III} coordination geometries are distorted square-pyramidal and octahedral, respectively. The structure of complex 5 is assumed to be a six-coordinate, distorted octahedral monomer. Variable-temperature solid-state magnetic susceptibility studies on complex 4 at 10.0 kG are reported.« less
The treatment of Mn{sub 3}O(O{sub 2}CPh){sub 6}(py){sub 2}(H{sub 2}O) with 2,2{prime}-biphenol (biphenH{sub 2}) and NEt{sub 3} in MeCN leads to formation of (NEt{sub 3}H){sub 2}(Mn(biphen){sub 2}(biphenH)) (2), and the crystal structure is reported. A similar reaction system using 3,3{prime}, 5,5{prime}-tetra-bromobiphenol leads to the product (NEt{sub 3}H){sub 2}(Mn(Br{sub 4}biphen){sub 2}(O{sub 2}CPh)) (3) whose IR spectrum suggests its structure to be similar to 2 with a chelating ({eta}{sup 2}) benzoate replacing the monodentate biphenH group. Treatment of complex 2 with 2,2{prime}-bipyriding (bpy) in CH{sub 2}CI{sub 2} yields a black solution: layering with hexanes and storage at {minus}20C leads to crystallization of Mn{sub 2}(biphen){sub 2}(biphenH)(byp){sub 2} (4) whereas storage at room temperature leads to crystallization of (bpyH)(Mn(biphen){sub 2}(bpy)) (5) The crystal structure of complex 4 is reported. The complex is mixed-valence (Mn{sup II},Mn{sup III}), and the structure consists of two Mn atoms bridged by two oxygen atoms from two biphen groups, the other oxygen atoms of which are terminally ligated to the Mn{sup III} center. Six-coordination of the latter is completed by a chelating bpy. The Mn{sup II} has a chelating bpy, and five-coordination is completed by a monodentate biphenH, the second oxygen of which is protonated as in 2. The Mn{sup II}more » and Mn{sup III} coordination geometries are distorted square-pyramidal and octahedral, respectively. The structure of complex 5 is assumed to be a six-coordinate, distorted octahedral monomer. Variable-temperature solid-state magnetic susceptibility studies on complex 4 at 10.0 kG are reported.« less