Several mononuclear ruthenium complexes containing bulky diphosphines have been easily prepared from acetate ruthenium precursors. The cyclohexyl complex [Ru(η²-OAc)₂(DCyPF)] (1-cy; DCyPF = 1,1′-bis(dicyclohexylphosphino)ferrocene) is synthesized from [Ru(η²-OAc)₂(PPh₃)₂] and DCyPF in toluene at reflux, whereas the ethylenediamine (en) derivatives trans-[Ru(η¹-OAc)₂(PP)(en)] (PP = 1,1′-bis(diisopropylphosphino)ferrocene (DiPPF) (2), DCyPF (3)) have been obtained in a one-pot reaction from [Ru(η²-OAc)₂(PPh₃)₂], PP, and en in n-heptane. Treatment of the isopropylphosphine complex [Ru(η²-OAc)₂(DiPPF)] (1-ip) with 2-(aminomethyl)pyridine (ampy) in methanol affords the isolation of a mixture of the cationic [Ru(η²-OAc)(DiPPF)(ampy)]OAc (5a) and cis-[Ru(η¹-OAc)₂(DiPPF)(ampy)] (5b) (4/1 molar ratio), via trans-[Ru(η¹-OAc)₂(DiPPF)(ampy)] (4) characterized at low temperature. The analogous cyclohexyl compound trans-[Ru(η¹-OAc)₂(DCyPF)(ampy)] (6), synthesized from [Ru(η²-OAc)₂(PPh₃)₂], DCyPF and ampy in heptane, slowly converts into [Ru(η²-OAc)(DCyPF)(ampy)]OAc (7) at RT. The monocarbonyl derivatives [Ru(η¹-OAc)(η²-OAc)(PP)(CO)] (PP = 1,3-bis(cyclohexylphosphino)propane (DCyPP) (8), (R)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldicyclohexylphosphine (Josiphos^cy) (9)) are obtained from [Ru(η¹-OAc)(η²-OAc)(PPh₃)₂(CO)] and the suitable diphosphine. Treatment of [Ru(η¹-OAc)(η²-OAc)(DiPPF)(CO)] (10) with phenylacetylene and in the presence of pyridine leads to the alkynyl complex [Ru(η²-OAc)(C≡CPh)(DiPPF)(CO)] (11), characterized by X-ray diffraction analysis. Protonation of 10 with 2 equiv of TFA at RT gives [Ru(η¹-OCOCF₃)(η²-OCOCF₃)(DiPPF)(CO)] (12). The dicarbonyl trans,cis-[Ru(η¹-OAc)₂(DiPPF)(CO)₂] (13) is obtained by reaction of 1-ip with CO (1 atm) in CH₂Cl₂, whereas the isomer cis,cis-[Ru(η¹-OAc)₂(DiPPF)(CO)₂] (14) can be prepared from carbonylation of 10. When 13 is heated in the solid state, 10 is formed by decarbonylation. These complexes promote the transfer hydrogenation of acetophenone in 2-propanol (S/C = 1000–2000) with NaOiPr (2 mol %), affording a TOF value of up to 81000 h^–1 for complex 9 at 30 °C. Complex 10 catalyzes the head-to-head dimerization of terminal alkynes to 1,4-enynes in toluene at reflux with high stereoselectivity for the kinetic Z isomer.

中文翻译：

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大体积乙酸二膦酯钌配合物：酮转移加氢和炔烃二聚反应中的合成及催化活性

容易从乙酸钌钌前体制备几种含有大体积二膦的单核钌配合物。环己基复杂的[Ru（η ² -OAc）₂（DCyPF）]（1- CY ; DCyPF = 1,1'-双（二环己基膦）二茂铁）从的[Ru（η合成² -OAc）₂（PPH ₃）₂ ]和DCyPF在回流甲苯，而乙二胺（烯）衍生物的反式- [茹（η ¹ -OAc）₂（PP）（烯）]（PP = 1,1'-双（二异丙基）二茂铁（d我PPF）（2），DCyPF（3））已经在从一个单釜反应中获得的[Ru（η ² -OAc）₂（PPH ₃）₂ ]，PP，和连接在Ñ庚烷。的异丙基膦配合物的[Ru（η的治疗² -OAc）₂（d我PPF）]（1- IP）与2-（氨基甲基）吡啶（AMPY）的甲醇，得到阳离子型的混合物的分离的[Ru（η ² -OAc）（d我PPF）（AMPY）] OAC（图5a）和顺式- [茹（η ¹ -OAc）₂（d我PPF）（AMPY）]（5B）（4/1摩尔比），通过反式-的[Ru（η ¹ -OAc）₂（d我PPF）（AMPY）]（4）其特征在于在较低的温度。类似环己基化合物的反式- [茹（η ¹ -OAc）₂（DCyPF）（AMPY）]（6）中，从合成的[Ru（η ² -OAc）₂（PPH ₃）₂ ]，DCyPF和在庚烷中AMPY，慢慢转换成的[Ru（η ² -OAc）（DCy​​PF）（AMPY）] OAC（7）在室温下。的单羰基衍生物的[Ru（η ¹ -OAc）（η ² -OAc）（PP）（CO）]（PP = 1,3-双（cyclohexylphosphino）丙烷（DCyPP）（8），（ř）-1 - [（小号）-2-（二环己基膦）二茂铁基] ethyldicyclohexylphosphine（Josiphos ^CY）（9从获得））的[Ru（η ¹ -OAc）（η ² -OAc）（PPH ₃）₂（CO） ]和合适的二膦。的[Ru（η的治疗¹ -OAc）（η ² -OAc）（d我PPF）（CO）]（10）与苯基乙炔和在吡啶引线的存在对炔复杂的[Ru（η ² -OAc）（ C≡CPh）（D i PPF）（CO）]（11），通过X射线衍射分析表征。的质子化10与在RT 2当量TFA的给出的[Ru（η ¹-OCOCF ₃）（η ² -OCOCF ₃）（d我PPF）（CO）]（12）。二羰基的反式，顺式- [茹（η ¹ -OAc）₂（d我PPF）（CO）₂ ]（13）通过下述物质反应得到1- IP用CO（1个大气压）的CH ₂氯₂，而异构体的顺式，顺式- [茹（η ¹ -OAc）₂（d我PPF）（CO）₂ ]（14）可从羰基化来制备10。当以固态加热13时，通过脱羰形成10。这些配合物促进了苯乙酮在2-丙醇（S / C = 1000–2000）中与NaO i Pr（2 mol％）的转移氢化，在30°C下提供的复合物9的TOF值高达81000 h ^–1。络合物10在回流下以动力学Z异构体的高立体选择性催化末端炔烃在甲苯中头对头二聚化为1，4-烯炔。