Synthesis and Reactivity of a Dithiolate-Bridged Ruthenium−Rhodium Heterobimetallic Dihydride Complex
Synthesis and Reactivity of a Dithiolate-Bridged Ruthenium−Rhodium Heterobimetallic Dihydride Complex
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DOI：
10.1021/om050871n
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发表时间：
2006-01
期刊：
影响因子：
2.8
通讯作者：
S. Takemoto;Daisuke Shimadzu;K. Kamikawa;†‡ and Hiroyuki Matsuzaka;R. Nomura
中科院分区：
文献类型：
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作者：
S. Takemoto;Daisuke Shimadzu;K. Kamikawa;†‡ and Hiroyuki Matsuzaka;R. Nomura
制备了新型二硫酸桥接Ru−Rh杂双金属二氢化物配合物[Cp*Rh(μ2-1,2- s2c6h4)(μ2-H)RuH(PPh3)2](2)，并研究了其与CO和炔烃的反应。用[RuHCl(PPh3)3]处理THF中的1,2-苯二硫酸铑络合物[Cp*Rh(1,2- s2c6h4)] (Cp* = η5-C5Me5)，生成氢化物和二硫酸桥接的Ru - Rh杂双金属络合物[Cp*Rh(μ2-1,2- s2c6h4)(μ2-H)RuCl(PPh3)2](1)，经KOH/i-PrOH处理后，进一步转化为二氢化物络合物[Cp*Rh(μ2-1,2- s2c6h4)(μ2-H)RuH(PPh3)2](2)。配合物2与CO反应生成二羰基配合物[Cp*Rh(μ2-1,2- s2c6h4)Ru(CO)2(PPh3)](3)。2与对甲基乙炔（2等价物）的反应是由炔的氢化和sp C−H键的氧化加成得到炔基氢化物配合物[Cp*Rh(μ2-1,2- s2c6h4)(μ2-H)Ru(C - c1 -p)(PPh3)2] （4a）。制备了类似的炔基氢化物配合物[Cp*Rh(μ2-1,2- s2c6h4)(μ2-H)Ru(C - CSiMe3)(PPh3)2] （4b）。配合物4a与…
The new dithiolate-bridged Ru−Rh heterobimetallic dihydride complex [Cp*Rh(μ2-1,2-S2C6H4)(μ2-H)RuH(PPh3)2] (2) has been prepared, and its reactions with CO and alkynes have been studied. Treatment of the rhodium 1,2-benzenedithiolate complex [Cp*Rh(1,2-S2C6H4)] (Cp* = η5-C5Me5) with [RuHCl(PPh3)3] in THF produces the hydride- and dithiolate-bridged Ru−Rh heterobimetallic complex [Cp*Rh(μ2-1,2-S2C6H4)(μ2-H)RuCl(PPh3)2] (1), which was further converted to the dihydride complex [Cp*Rh(μ2-1,2-S2C6H4)(μ2-H)RuH(PPh3)2] (2) upon treatment with KOH/i-PrOH. Complex 2 reacts with CO to give the dicarbonyl complex [Cp*Rh(μ2-1,2-S2C6H4)Ru(CO)2(PPh3)] (3). Reaction of 2 with p-tolylacetylene (2 equiv) proceeds with hydrogenation of the alkyne and subsequent oxidative addition of the sp C−H bond to give the alkynyl hydride complex [Cp*Rh(μ2-1,2-S2C6H4)(μ2-H)Ru(C⋮CTol-p)(PPh3)2] (4a). The analogous alkynyl hydride complex [Cp*Rh(μ2-1,2-S2C6H4)(μ2-H)Ru(C⋮CSiMe3)(PPh3)2] (4b) has also been prepared. Complex 4a reacts with...