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Heavier group 2 metal complexes with a flexible scorpionate ligand based on 2-mercaptopyridine

机译：具有基于2-巯基吡啶的柔性蝎子配体的重2族金属配合物

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We report the synthesis of novel alkaline earth metal complexes [k(2)-SS-(Bmp)(2)M(THF)(n)] [M = Ca (2), Sr (3) n = 2; M = Ba (4), n = 3] of a flexible dihydrobis(2-thiopyridone) borate (Bmp) ligand based on 2-mercaptopyridine. Complexes 2-4 were isolated in good yield by the reaction between sodium dihydrobis(2-thiopyridone) borate, [{(Bmp) Na(THF)}(2)](n) (1) and the corresponding alkaline earth metal diiodides in toluene at ambient temperature. The solid-state structures of the strontium and barium complexes, complexes 3 and 4 respectively, were established using single-crystal X-ray diffraction analysis. The solid-state structure of sodium complex 1 was also confirmed using X-ray techniques. The solid-state structures of complexes 3 and 4 revealed that the Bmp ligand coordinates through sulphur atoms to the metal ions in k(2) fashion. The strontium ion is attached symmetrically and the barium ion is asymmetrically linked with the Bmp ligand, manifesting the 2-thiopyridone and pyridine-2-thiolate tautomeric form of the Bmp ligand. The strontium ion in complex 3 adopts a distorted octahedral geometry whereas the geometry around the barium ion can best be described as a distorted pentagonal bipyramidal. Both complexes 3 and 4 also have a short B center dot center dot center dot H center dot center dot center dot M interaction due to the presence of the BH2 group in the ligand. In the solid state, sodium complex 1 is polymeric in nature and in the asymmetric unit each sodium ion is bonded to two sulphur atoms through eta(1) and mu(2) modes. The adjacent BH2 group is also linked with each sodium ion through hydrogen atoms via mu(2) and eta(1).
机译：我们报告了新型碱土金属配合物的合成[k（2）-SS-（Bmp）（2）M（THF）（n）] [M = Ca（2），Sr（3）n = 2; M ＝ Ba（4），n ＝ 3]基于2-巯基吡啶的柔性二氢双（2-硫代吡啶酮）硼酸酯（Bmp）配体。通过二氢双（2-硫代吡啶酮）硼酸钠，[{（Bmp）Na（THF）}（2）]（n）（1）和相应的碱土金属二碘化物的反应，高收率分离出配合物2-4。甲苯在环境温度下。锶和钡配合物，分别为配合物3和4，的固态结构是使用单晶X射线衍射分析建立的。钠配合物1的固态结构也使用X射线技术确认。配合物3和4的固态结构表明Bmp配体通过硫原子以k（2）的方式与金属离子配位。锶离子对称连接，钡离子与Bmp配体不对称连接，表现出Bmp配体的2-硫代吡啶酮和吡啶-2-硫醇盐互变异构形式。配合物3中的锶离子采用扭曲的八面体几何形状，而钡离子周围的几何形状最好描述为扭曲的五边形双锥体。由于配体中存在BH 2基，因此配合物3和4也具有短的B中心点中心点中心点H中心点中心点中心点M相互作用。在固态状态下，钠络合物1本质上是聚合的，在不对称单元中，每个钠离子通过eta（1）和mu（2）模式与两个硫原子键合。相邻的BH2基团还通过mu（2）和eta（1）通过氢原子与每个钠离子连接。

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