Die fördernde Rolle von Phosphinoester-Liganden bei der Synthese neutraler Carben-, Vinyliden- und Allenyliden-Ruthenium(II)-Komplexe†
Die fördernde Rolle von Phosphinoester-Liganden bei der Synthese neutraler Carben-, Vinyliden- und Allenyliden-Ruthenium(II)-Komplexe†
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Die fördernde Rolle von Phosphinoester-Liganden bei der Synthese 中性剂 Carben-、Vinyliden- 和 Allenyliden-Ruthenium(II)-Komplexe†
DOI：
10.1002/cber.19951280108
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发表时间：
1995
期刊：
影响因子：
--
通讯作者：
J. Wolf
中科院分区：
文献类型：
--
作者：
H. Werner;A. Stark;C. Steinert;J. Wolf
Vinylidene Transition‐Metal Complexes, XXXV[1]. - The Supporting Role of Phosphino Ester Ligands for the Synthesis of Neutral Carbene, Vinylidene and Allenylidene Ruthenium(II) ComplexesThe reaction of [RuCl2(PPh3)3] (1) with the phosphino estersiPr2P(CH2)nCO2R (2–4) leads to complete (n= 1; R CH3, C2H5) or partial (n= 2; R CH3) displacement of the PPh3ligands and formation of the octahedral ruthenium(II) complexes [RuCl2{k2(P,O)‐iPr2PCH2CO2R}2] (5, 6) and [RuCl2(PPh3){k(P)‐iPr2PCH2CH2CO2Me}{k2(P,O)‐iPr2PCH2CH2CO2Me}] (7). Treatment of5with LiBr and LiI affords the dibromo‐ and diiodoruthenium derivatives8and9.While compound5reacts with CO and SO2by cleavage of one Ru-O bond to yield the 1:1 adducts [RuCl2(L){k(P)‐iPr2PCH2CO2Me}{k2(P,O)‐iPr2PCH2CO2Me}] (10, 11), the reaction of the dibromo derivative8with CO in solution gives the dicarbonyl complex [RuBr2(CO)2{k(P)‐iPr2PCH2CO2Me}2](13). If CO is passed over8in the solid state, the corresponding monocarbonyl compound14is formed. The hydridoruthenium(II) complex16, which is obtained from equimolar amounts of [RuHCl(CO)(PiPr3)2] (15) and2, reacts with HCCMe by insertion to give the vinyl derivative [RuCl{E-CHCHMe}(CO)(PiPr3){k2(P,O)‐iPr2CH2CO2Me}] (17). Treatment of5with HC̊' (R' H, Me,tBu, Ph) and of6, 8, 9with HCCPh affords upon photochemical activation the octahedral vinylidene complexes [RuX2‐(CCHR){k(P)‐iPr2PCH2CO2R}{k2(P,O)‐iPr2PCH2CO2R}] (18–21and23–25) in good to excellent yield. At room temperature, these compounds (with the exception of25) are highly fluxional in solution. From31P‐NMR measurements, the free energies of activation ΔG‡for the intramolecular rearrangement have been determined. Whereas the reaction of 5 with HCČH2CH2OH leads to the carbene complex30containing the cyclic oxycarbene :C(CH2)3O as ligand, the functionalized vinylidene derivatives31and32are formed on treatment of5with aryl‐substituted alkynols HC≡RR'OH (R Ph, R' Ph,o‐Tol). These react in toluene solution at 80°C by elimination of water to give the allenylidene complexes [RuCl2(CCCRR'){k(P)‐iPr2PCH2CO2Me}{k2(P,O)‐iPr2PCH2CO2Me}] (33, 34). The X‐ray structure analysis of33reveals atransdisposition of the chloro ligands, the phosphorus atoms as well as of one CO oxygen and the α‐C atom of the allenylidene unit. Compound33reacts with CO, CNtBu and pyridine to give the 1:1 adducts [RuCl2(L)(CCCPh2){k(P)‐iPr2PCH2CO2Me}2] (35–37) and with HCl by attack on the central CC bond to yield the vinylcarbene complex [RuCl2(C(Cl)CHCRR'){k((P)‐iPr2‐PCH2CO2Me}{k2(P,O)‐iPr2PCH2CO2Me}] (38). The preparation of the phosphino ketoneiPr2PCH2C(O)CH3(40) and its ruthenium complexes41and42is briefly described.
Vinylidene Transition‐Metal Complexes, XXXV[1]. — The Supporting Role of Phosphino Ester Ligands for the Synthesis of Neutral Carbene, Vinylidene and Allenylidene Ruthenium(II) ComplexesThe reaction of [RuCl2(PPh3)3] (1) with the phosphino estersiPr2P(CH2)nCO2R (2–4) leads to complete (n= 1; R CH3, C2H5) or partial (n= 2; R CH3) displacement of the PPh3ligands and formation of the octahedral ruthenium(II) complexes [RuCl2{k2(P,O)‐iPr2PCH2CO2R}2] (5, 6) and [RuCl2(PPh3){k(P)‐iPr2PCH2CH2CO2Me}{k2(P,O)‐iPr2PCH2CH2CO2Me}] (7). Treatment of5with LiBr and LiI affords the dibromo‐ and diiodoruthenium derivatives8and9.While compound5reacts with CO and SO2by cleavage of one Ru—O bond to yield the 1:1 adducts [RuCl2(L){k(P)‐iPr2PCH2CO2Me}{k2(P,O)‐iPr2PCH2CO2Me}] (10, 11), the reaction of the dibromo derivative8with CO in solution gives the dicarbonyl complex [RuBr2(CO)2{k(P)‐iPr2PCH2CO2Me}2](13). If CO is passed over8in the solid state, the corresponding monocarbonyl compound14is formed. The hydridoruthenium(II) complex16, which is obtained from equimolar amounts of [RuHCl(CO)(PiPr3)2] (15) and2, reacts with HCCMe by insertion to give the vinyl derivative [RuCl{E—CHCHMe}(CO)(PiPr3){k2(P,O)‐iPr2CH2CO2Me}] (17). Treatment of5with HC̊' (R' H, Me,tBu, Ph) and of6, 8, 9with HCCPh affords upon photochemical activation the octahedral vinylidene complexes [RuX2‐(CCHR){k(P)‐iPr2PCH2CO2R}{k2(P,O)‐iPr2PCH2CO2R}] (18–21and23–25) in good to excellent yield. At room temperature, these compounds (with the exception of25) are highly fluxional in solution. From31P‐NMR measurements, the free energies of activation ΔG‡for the intramolecular rearrangement have been determined. Whereas the reaction of 5 with HCČH2CH2OH leads to the carbene complex30containing the cyclic oxycarbene :C(CH2)3O as ligand, the functionalized vinylidene derivatives31and32are formed on treatment of5with aryl‐substituted alkynols HC≡RR'OH (R Ph, R' Ph,o‐Tol). These react in toluene solution at 80°C by elimination of water to give the allenylidene complexes [RuCl2(CCCRR'){k(P)‐iPr2PCH2CO2Me}{k2(P,O)‐iPr2PCH2CO2Me}] (33, 34). The X‐ray structure analysis of33reveals atransdisposition of the chloro ligands, the phosphorus atoms as well as of one CO oxygen and the α‐C atom of the allenylidene unit. Compound33reacts with CO, CNtBu and pyridine to give the 1:1 adducts [RuCl2(L)(CCCPh2){k(P)‐iPr2PCH2CO2Me}2] (35–37) and with HCl by attack on the central CC bond to yield the vinylcarbene complex [RuCl2(C(Cl)CHCRR'){k((P)‐iPr2‐PCH2CO2Me}{k2(P,O)‐iPr2PCH2CO2Me}] (38). The preparation of the phosphino ketoneiPr2PCH2C(O)CH3(40) and its ruthenium complexes41and42is briefly described.