C-H Activation of Cp Ligand Coordinated to Ruthenium Center: Synthesis and Reactivity of a Thiolate-Bridged Diruthenium Complex Featuring Fulvene-like Cp Ligand
C-H Activation of Cp Ligand Coordinated to Ruthenium Center: Synthesis and Reactivity of a Thiolate-Bridged Diruthenium Complex Featuring Fulvene-like Cp Ligand
复制标题
与钌中心配位的 Cp 配体的 C-H 活化：具有类富烯 Cp 配体的硫醇桥联钌络合物的合成和反应性
DOI：
10.1021/acs.organomet.7b00091
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发表时间：
2017
期刊：
影响因子：
2.8
通讯作者：
Qu Jingping
中科院分区：
文献类型：
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作者：
Ji Xiaoxiao;Yang Dawei;Tong Peng;Li Jianzhe;Wang Baomin;Qu Jingping
在弱碱Et3N存在下，[Cp*Ru(μ-η2：η4-bdt)RuCp*](1，Cp*=η5-C5Me5；BDT=苯-1，2-二硫酸酯)与2当量的FC·Pf6反应，使配位的CP*中的一个甲基容易被C-H活化，得到富烯类CP*配体[(η5：η1-C5Me4CH2)Ru(μ-η2：η4-bdt)RuCp*][Pf6](2[Pf6])，其中富烯类CP*部分最好地被描述为η5：η1-四甲基富烯配体。当络合物2[Pf6]受到盐酸的亲电攻击时，类富烯的Cp*配体随着氯桥配合物[Cp*Ru(μ-η2：η2-bdt)(μ-Cl)RuCp*][Pf6](3[Pf6])的形成而重新生成完整的Cp*基团。当配合物2[PF6]与碘反应时，Cp*甲基发生官能化反应，以较高的产率得到Cp*环碘取代络合物[(η5-C5Me4CH2I)Ru(t-I)(μ-η2:η4-bdt)RuCp*][PF6](4[PF6])。重要的是，2[Pf6]与元素硫的反应导致了S8的S-S键的断裂，S8在Ru-次甲基键上插入了一个二硫键片段，生成了[(η5：η1-C5Me4CH2S2)Ru(μ-η2：η4-bdt)RuCp*][Pf6](5[Pf6])，这为富烯类CP*配体2[Pf6]的结构描述提供了强有力的化学证据。最引人注目的是，CO和tBuNC处理2[Pf6]，导致[Ru(μ-η5:η1-C5Me4CH2)(t-CO)(μ-η2:η2-bdt)RuCp*][PF6](6[Pf6])和[Ru(μ-η5:η1-C5Me4CH2)(t-tBuNC)(μ-η2:η2-bdt)RuCp*][PF6](7[Pf6])的配位方式从一个Ru中心上的η5：η1转变为两个Ru中心之间的μ-η5：η1。
In the presence of weak base Et3N, the interaction of [Cp*Ru(μ-η2:η4-bdt)RuCp*] (1, Cp* = η5-C5Me5; bdt = benzene-1,2-dithiolate) with 2 equiv of Fc·PF6resulted in facile C–H activation of one methyl group in coordinated Cp* to give a diruthenium complex with a fulvene-like Cp* ligand, [(η5:η1-C5Me4CH2)Ru(μ-η2:η4-bdt)RuCp*][PF6] (2[PF6]), in which the fulvene-like Cp* moiety is best described as an η5:η1-tetramethylfulvene ligand based on1H NMR and13C NMR spectroscopic data. When complex2[PF6]was subjected to the electrophilic attack of HCl, an intact Cp* group was regenerated from the fulvene-like Cp* ligand along with the formation of the chloride bridged complex [Cp*Ru(μ-η2:η2-bdt)(μ-Cl)RuCp*][PF6] (3[PF6]). While complex2[PF6]reacted with iodine, functionalization of a Cp* methyl group was realized to give a Cp* ring iodine-substituted complex [(η5-C5Me4CH2I)Ru(t-I)(μ-η2:η4-bdt)RuCp*][PF6] (4[PF6]) in excellent yield. Importantly, reaction of2[PF6]with elemental sulfur led to the S–S bond fission of S8following insertion of a disulfide fragment into the Ru–methylene bond to produce [(η5:η1-C5Me4CH2S2)Ru(μ-η2:η4-bdt)RuCp*][PF6] (5[PF6]), which provides strong chemical evidence for structural description of the fulvene-like Cp* ligand in2[PF6]. Most strikingly, treatment of2[PF6]with CO andtBuNC resulted in the coordination mode switch of the fulvene-like Cp* ligand from η5:η1on one ruthenium center to μ-η5:η1between two ruthenium centers to afford [Ru(μ-η5:η1-C5Me4CH2)(t-CO)(μ-η2:η2-bdt)RuCp*][PF6] (6[PF6]) and [Ru(μ-η5:η1-C5Me4CH2)(t-tBuNC)(μ-η2:η2-bdt)RuCp*][PF6] (7[PF6]), respectively.