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首页> 外文期刊>Acta crystallographica. Section C, Structural chemistry. >Comparison of thallium(I) complexes with mesityl-substituted tris(pyrazolyl)hydroborate ligands, [Tl{HB(3-Ms-5-Mepz)_3}] and [Tl{HB(3-Ms-5-Mepz)_2(3-Me-5-Mspz)}]
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Comparison of thallium(I) complexes with mesityl-substituted tris(pyrazolyl)hydroborate ligands, [Tl{HB(3-Ms-5-Mepz)_3}] and [Tl{HB(3-Ms-5-Mepz)_2(3-Me-5-Mspz)}]

机译：铊（I）复合物与乙基取代的Tris（吡唑基）水硼酸盐配体的比较[T1 {Hb（3-MS-5-MEPZ）_3}]和[T1 {Hb（3-MS-5-Mepz）_2（ 3-ME-5-MSPZ）}]

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摘要

Tris(pyrazolyl)borate (scorpionate) ligands can be considered as the most prolific ligands in contemporary coordination chemistry due to the availability of various steric and electronic substituents at the pyrazolyl rings that allow fine-tuning of the open-coordination site for metal centres. The thallium(I) complexes of anionic tridentate-chelating scorpionate ligands, namely [tris(3-mesityl-5-methyl-1H/-pyrazol-1-yl-κN~2)hydroborato]thallium(I) monohydrate, [T1(C_39H_46BN_6)]-H_2O, (I), and [bis(3-mesityl-5-methyl-1H-pyrazol-1-yl-κN~2)(5-mesityl-3-methyl-1H-pyrazol-1-yl-κN~2)hydroborato]thallium(I), [Tl(C_39H_46BN_6)], (II), show a {Tl~IN_3} coordination, with average Tl~I—N bond lengths of 2.53 and 2.55 A in (I) and (II), respectively. The overall Tl~I coordination geometry is distorted trigonal pyramidal, with the average N—Tl~I—N angle being approximately 73° for both. The dihedral angle between the planes of the pyrazolyl and benzene rings of the mesityl group is 82° in (I), while the corresponding angles in (II) are in the range 64-104°. The structural differences between the two ligands are expected to contribute to the different reactivities of the transition metal coordination complexes towards activation of small molecules such as dioxygen and ethylene.
机译：硼酸硼（蝎子）配体可被认为是当代配位化学中最多增殖的配体，因为吡唑克朗环的可用性，允许微调金属中心的开放式配位部位进行微调。阴离子三齿 - 螯合蝎子配体的铊（I）复合物，即[Tris（3-千分比-5-甲基-1H / -pyrazol-1-Y1-κ〜2）巯基（I）一水合物，[T1（ C_39H_46BN_6）] - H_2O，（I）和[双（3-千分比 - 5-甲基-1H-吡唑-1-基-1-κN〜2）（5-千分比二 - 3-甲基-1H-吡唑-1-基-κN〜2）氢硼酸盐]铊（I），[T1（C_39H_46BN_6）]，（II），显示为（I）的平均T1〜I-N键长度（I） （ii）分别。整体TL〜I协调几何形状是扭曲的三角形金字塔，平均n-T1〜I-n角对于两者约为73°。吡唑基的平面与叶片基团的平面之间的二偏角角在（i）中为82°，而（II）的相应角度在64-104°的范围内。预计两个配体之间的结构差异将有助于过渡金属配位复合物的不同反应性朝向激活的小分子如二氧化乙烯和乙烯。

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