Benzannulated tris(2-mercapto-1-imidazolyl)hydroborato ligands: tetradentate κ4-S3H binding and access to monomeric monovalent thallium in an [S3] coordination environment.
Benzannulated tris(2-mercapto-1-imidazolyl)hydroborato ligands: tetradentate κ4-S3H binding and access to monomeric monovalent thallium in an [S3] coordination environment.
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DOI：
10.1039/c3dt52418c
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发表时间：
2014-01-21
期刊：
影响因子：
--
通讯作者：
Parkin G
中科院分区：
文献类型：
--
作者：
Rong Y;Palmer JH;Parkin G
通过NaBH_4与1-叔丁基-1，3-二氢-2H-苯并咪唑-2-酮的反应合成了苯并环化的三（巯基咪唑基）硼氢化钠配合物[TmButBenz]Na，而通过KBH_4与1-甲基-1，3-二氢-2H-苯并咪唑-2-酮的反应合成了[TmMeBenz]K。用X射线衍射法测定了溶剂化加合物{[TmButBenz]Na（THF）}2（μ-THF）2和[TmMeBenz]K（OCMe 2）3的分子结构，表明[TmR]配体在这些配合物中采用与{[TmMeBenz]Na}2（μ-THF）3不同的配位方式.具体而言，虽然钠络合物{[TmMeBenz]Na}2（μ-THF）3的[TmMeBenz]配体采用κ3-S3配位模式，但钾络合物[TmMeBenz]K（OCMe 2）3采用最不常见的反向κ4-S3 H配位模式，其中钾以线性K···H-B方式结合所有三个硫供体和B-H基团的氢。此外，[TmButBenz]Na（THF）}2（μ-THF）2的[TmButBenz]配体采用κ3-S2 H配位模式，从而证明该配体系统的灵活性。通过[TmMeBenz]Na和[TmButBenz]Na与TlOAc的相应反应，得到了一价铊化合物[TmMeBenz]Tl和[TmButBenz]Tl。X射线衍射表明，[TmMeBenz]Tl和[TmButBenz]Tl的[TmRBenz]配体的三个硫供体与铊螯合。这种配位模式与其他[TmR]Tl化合物中的配位模式形成鲜明对比，其他[TmR]Tl化合物作为双核分子存在，其中两个硫供体与不同的铊中心配位。因此，这一观察结果提供了进一步的证据，证明苯并环化促进了该系统中的κ3-S3配位。
The benzannulated tris(mercaptoimidazolyl)borohydride sodium complex, [TmButBenz]Na, has been synthesized via the reaction of NaBH4 with 1-tert-butyl-1,3-dihydro-2H-benzimidazole-2-thione, while [TmMeBenz]K has been synthesized via the reaction of KBH4 with 1-methyl-1,3-dihydro-2H-benzimidazole-2-thione. The molecular structures of the solvated adducts, {[TmButBenz]Na(THF)}2(μ-THF)2 and [TmMeBenz]K(OCMe2)3, have been determined by X-ray diffraction, which demonstrates that the [TmR] ligands in these complexes adopt different coordination modes to that in {[TmMeBenz]Na}2(μ-THF)3. Specifically, while the [TmMeBenz] ligand of the sodium complex {[TmMeBenz]Na}2(μ-THF)3 adopts a κ3-S3 coordination mode, the potassium complex [TmMeBenz]K(OCMe2)3 adopts a most uncommon inverted κ4-S3H coordination mode in which the potassium binds to all three sulfur donors and the hydrogen of the B–H group in a linear K•••H–B manner. Furthermore, the [TmButBenz] ligand of {[TmButBenz]Na(THF)}2(μ-THF)2 adopts a κ3-S2H coordination mode, thereby demonstrating the flexibility of this ligand system. The monovalent thallium compounds, [TmMeBenz]Tl and [TmButBenz]Tl, have been obtained via the corresponding reactions of [TmMeBenz]Na and [TmButBenz]Na with TlOAc. X-ray diffraction demonstrates that the three sulfur donors of the [TmRBenz] ligands of both [TmMeBenz]Tl and [TmButBenz]Tl chelate to thallium. This coordination mode is in marked contrast to that in other [TmR]Tl compounds, which exist as dinuclear molecules wherein two of the sulfur donors coordinate to different thallium centers. As such, this observation provides further evidence that benzannulation promotes κ3-S3 coordination in this system.
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影响因子：
2.6
作者：
Bakbak, S;Bhatia, VK;Rabinovich, D
通讯作者：
Rabinovich, D
影响因子：
15
作者：
Bridgewater, BM;Parkin, G
通讯作者：
Parkin, G
影响因子：
4.4
作者：
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通讯作者：
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影响因子：
4
作者：
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通讯作者：
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影响因子：
4.9
作者：
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通讯作者：
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