Synthesis, crystal structure and magnetic properties of the complex [ReCl3(tppz)]center dot MeCN

Palion-Gazda J.; Gryca I.; Machura B.; Lloret Francesc; Julve Miguel

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Synthesis, crystal structure and magnetic properties of the complex [ReCl3(tppz)]center dot MeCN

机译：复杂的合成，晶体结构和磁性[RECL3（TPPZ）]中心点MECN

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The reaction of the starting materials [(ReCl3)-Cl-III(MeCN)(PPh3)(2)] or [(ReOCl3)-O-V(PPh3)(2)] with 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz) in acetonitrile yielded the Re(III) complex [ReCl3(tppz)]center dot MeCN (1). This complex crystallizes in the monoclinic space group P2(1)/n and its crystal structure consists of neutral mononuclear entities with meridional geometry of the chloride ligands, and the six-coordination of the Re(III) ion being completed by the tridentate tppz ligand. Each metal centre exhibits a highly distorted octahedral coordination with Re-Cl and Re-N-tppz bond lengths covering the ranges 2.3590(9)-2.3606(8) and 1.971(2)-2.096(2) angstrom, respectively. The magnetic properties of 1 have been investigated in the temperature range 1.9-290 K. They are characteristic of a six-coordinate Re(III) mononuclear complex with d(4) low-spin (T-3(1) ground state). The magnetic data of 1 are discussed through a deep analysis of the influence of the ligand-field, spin-orbit coupling, tetragonal distortion and covalency effects. The second-order Zeeman effect between the non-magnetic ground state (M-J = 0) and higher energy levels (M-J not equal 0) determines the magnetic susceptibility of 1, the value of the temperature-independent paramagnetic susceptibility being 3378 x 10(-6) cm(3) mol(-1). This value compares well with those reported for other structurally characterized Re(III) complexes.

机译：起始材料[（RECL3）-CL-III（MECN）（PPH3）（2）]或[（REOCL3）-OV（PPH3）]的反应含有2,3,5,6-四（2 - 乙腈中的吡啶基（TPPZ）产生RE（III）复合物[RECL3（TPPZ）]中心点MECN（1）。该复合物在单斜视空间组P2（1）/ N中结晶，其晶体结构由中性单核实体组成，其中氯化物配体的子宫内饰和Re（III）离子的六个协调由Trientate TPPZ配体完成。每个金属中心具有高度扭曲的八面体协调，其覆盖范围2.3590（9）-2.3606（8）和1.971（2）-2.096（2）埃埃斯特朗姆的RE-CL和RE-N-TPPZ键长。已经在1.9-290k的温度范围内研究了1的磁性。它们是具有D（4）低旋转（T-3（1）地态）的六坐标Re（III）单核络合物的特征。通过深入分析配体场，旋转轨道耦合，四方变形和共价效应的深度分析来讨论1的磁性数据。在非磁场 - 态（MJ = 0）和更高的能级（MJ不等于0）之间的二阶栖息效应决定了1的磁化率，温度无关的顺磁性敏感度为3378 x 10（ - 6）cm（3）mol（-1）。该值与其他结构表征RE（III）复合物报告的那些相比良好。

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《RSC Advances》 |2015年第123期|共7页
作者
Palion-Gazda J.; Gryca I.; Machura B.; Lloret Francesc; Julve Miguel;
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Univ Silesia Inst Chem Dept Crystallog PL-40006 Katowice Poland;

Univ Silesia Inst Chem Dept Crystallog PL-40006 Katowice Poland;

Univ Silesia Inst Chem Dept Crystallog PL-40006 Katowice Poland;

Univ Valencia Fac Quim Inst Ciencia Mol ICMol Dept Quim Inorgan Valencia 46980 Spain;

Univ Valencia Fac Quim Inst Ciencia Mol ICMol Dept Quim Inorgan Valencia 46980 Spain;

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中图分类化学;
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Synthesis, crystal structure and magnetic properties of the complex [ReCl3(tppz)]center dot MeCN

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