Ruthenium and Rhodium Complexes with Thiolate-Containing Pincer Ligands Produced by C−S Bond Cleavage of Pyridyl-Substituted Dibenzothiophenes
Ruthenium and Rhodium Complexes with Thiolate-Containing Pincer Ligands Produced by C−S Bond Cleavage of Pyridyl-Substituted Dibenzothiophenes
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DOI：
10.1021/om8003916
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发表时间：
2008-08
期刊：
影响因子：
2.8
通讯作者：
M. Shibue;M. Hirotsu;T. Nishioka;I. Kinoshita
中科院分区：
文献类型：
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作者：
M. Shibue;M. Hirotsu;T. Nishioka;I. Kinoshita
4-（2′-吡啶基）二苯并噻吩（PyDBT）与钌羰基簇合物[Ru 3（CO）12]反应，得到双钌配合物[Ru（μ-PyBPT-κ 3 N，C，S）（CO）2]2（1），其中PyBPT表示3′-（2′′-吡啶基）-1，1 ′-联苯-2-硫醇的二价阴离子。三齿-N，C，S PyBPT配体提供由六元硫杂钌配体和五元氮杂钌配体组成的钳形结构。1中的含硫醇盐的NCS钳形配体是通过裂解PyDBT中与吡啶基相邻的碳硫键产生的。4-（4′-甲基-2 ′-吡啶基）二苯并噻吩（4-MePyDBT）和4-（6′-甲基-2 ′-吡啶基）二苯并噻吩（6-MePyDBT）的相应反应分别得到具有相同钳形骨架的双钌配合物[Ru（μ-4-MePyBPT-κ 3 N，C，S）（CO）2]2（2）和[Ru（μ-6-MePyBPT-κ 3 N，C，S）（CO）2]2（3）。3的形成要慢得多，证明了通过吡啶基与Ru的初始配位或形成N，S-螯合物结构的反应路径。事实上，PyDBT显示了螯合...
Treatment of 4-(2′-pyridyl)dibenzothiophene (PyDBT) with the ruthenium carbonyl cluster [Ru3(CO)12] gave the diruthenium(II) complex [Ru(μ-PyBPT-κ3N,C,S)(CO)2]2 (1), where PyBPT denotes a dianion of 3′-(2′′-pyridyl)-1,1′-biphenyl-2-thiol. The tridentate-N,C,S PyBPT ligand provides a pincer structure consisting of a six-membered thiaruthenacycle and a five-membered azaruthenacycle. The thiolate-containing NCS pincer ligand in 1 is produced by cleavage of a carbon−sulfur bond adjacent to a pyridyl group in PyDBT. The corresponding reactions using 4-(4′-methyl-2′-pyridyl)dibenzothiophene (4-MePyDBT) and 4-(6′-methyl-2′-pyridyl)dibenzothiophene (6-MePyDBT) afforded the diruthenium(II) complexes with the same pincer framework [Ru(μ-4-MePyBPT-κ3N,C,S)(CO)2]2 (2) and [Ru(μ-6-MePyBPT-κ3N,C,S)(CO)2]2 (3), respectively. The much slower formation of 3 certifies the reaction path through the initial coordination of the pyridyl group to Ru or the formation of an N,S-chelate structure. Indeed, PyDBT showed the chelatin...