High-frequency EPR study of a new mononuclear manganese(III) complex:. [(terpy)Mn(N3)3] (terpy = 2,2':6',2''-terpyridine).
High-frequency EPR study of a new mononuclear manganese(III) complex:. [(terpy)Mn(N3)3] (terpy = 2,2':6',2''-terpyridine).
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新型单核锰（III）配合物的高频 EPR 研究：
DOI：
10.1021/ic001118j
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发表时间：
2001
影响因子：
4.6
通讯作者：
Collomb,MN
中科院分区：
文献类型：
--
作者：
Limburg,J;Vrettos,JS;Crabtree,RH;Brudvig,GW;dePaula,JC;Hassan,A;Barra,AL;Duboc-Toia,C;Collomb,MN
报道了[（三联吡啶）Mn Ⅲ（N3）3]配合物1的分离和结构表征（三联吡啶= 2，2 '：6'，2 "-三联吡啶）。配合物1是混价二聚体[（terpy）（H_2O）MnIII（O）_2MnIV（OH_2）（terpy）]（NO_3）_3与NaN_3反应的产物，属三斜晶系，空间群P_1，a= 8.480（1）°，B= 8.9007（2）°，c= 12.109（2）°，α = 93.79（1）°，β = 103.17（1）°，γ = 103.11（1）°，Z = 2。配合物1表现出六配位高自旋Mn（III）八面体特征的Jahn-Teller畸变。进行了振动光谱研究。配合物1的νasym（N3）模在红外光谱中表现为2035 cm-1处的强带，在2072 cm-1处较弱;在拉曼光谱中表现为2071 cm-1处的强带，在2046 cm-1处较弱的宽带。使用高场和高频EPR研究（190−475 GHz）研究了络合物1的电子性质。不同的自旋哈密顿参数已被确定（D= −3.29（±0.01）cm-1，E= 0.48（±0.01）cm-1，E '= 0.53（±0.01）cm-1，gx= 2.00（±0.005），戈伊= 1.98（±0.005），gz= 2.01（±0.005））。这些参数与在晶体结构中观察到的络合物1的几何形状一致，aD< 0与拉长的畸变有关，并且E/D的值接近0.2，正如从高度畸变的八面体所预期的。的两个值的E-参数的解释由两个略有不同的结构形式的复杂1的晶格中的存在。第二个假设被探索来解释实验数据。模拟的计算是考虑到由于复数1的低对称性，gandDtensors不是共线的。在这种情况下，自旋哈密顿参数为D = −3.29（±0.01）cm-1，E= 0.51（±0.01）cm-1，gx= 2.00（±0.005），戈伊= 1.98（±0.005），gz = 2.01（±0.005）。
The isolation and structural characterization of [(terpy)MnIII(N3)3], complex1, is reported (terpy = 2,2‘:6‘,2‘ ‘-terpyridine). Complex1, a product of the reaction between the mixed-valence dimer [(terpy)(H2O)MnIII(O)2MnIV(OH2)(terpy)](NO3)3and NaN3, crystallizes in a triclinic system, space groupP1̄,a= 8.480(1) Å,b= 8.9007(2) Å,c= 12.109(2) Å, α = 93.79(1)°, β = 103.17(1)°, γ = 103.11(1)°, andZ= 2. Complex1exhibits a Jahn−Teller distortion of the octahedron characteristic of a six-coordinated high-spin Mn(III). A vibrational spectroscopic study was performed. The νasym(N3) mode of complex1appears in the IR as a strong band at 2035 cm-1with a less intense feature at 2072 cm-1, and in the FT-Raman as a strong band at 2071 cm-1with a weaker broad band at 2046 cm-1. The electronic properties of complex1were investigated using a high-field and high-frequency EPR study (190−475 GHz). The different spin Hamiltonian parameters have been determined (D= −3.29 (±0.01) cm-1,E= 0.48 (±0.01) cm-1,E‘= 0.53 (±0.01) cm-1,gx= 2.00 (±0.005),gy= 1.98 (±0.005),gz= 2.01 (±0.005)). These parameters are in agreement with the geometry of complex1observed in the crystal structure, aD< 0 related to the elongated distortion, and a value ofE/Dclose to 0.2 as expected from the highly distorted octahedron. The two values of theE-parameter are explained by the presence of two slightly different structural forms of complex1in the crystal lattice. A second hypothesis was explored to explain the experimental data. The calculation for the simulation was done taking into account that thegandDtensors are not collinear due to the low symmetry of complex1. In that case, the spin Hamiltonian parameters found areD= −3.29 (±0.01) cm-1,E= 0.51 (±0.01) cm-1,gx= 2.00 (±0.005),gy= 1.98 (±0.005), andgz= 2.01 (±0.005).