Isomerization Processes on Organoruthenium Complexes Bearing κ2(P,C)‐Bidentate Ligands Generated Through Nucleophilic Addition to Coordinated Alkenyl Phosphanes

다국어 초록 (Multilingual Abstract)

Nucleophilic attack on complex [RuCl(η6‐C10H14){κ3(P,C,C)‐Ph2PCH2CH=CH2}][BPh4] (2) takes place, either to the metal or to the coordinated olefin depending on the nucleophile and the reaction conditions. The nucleophilic attack of phosphanes on the coordinated olefin leads diastereoselectively to complexes [RuCl(η6‐C10H14){ĸ2(P,C)‐Ph2PCH2CH(PR3)CH2}]+ bearing κ2(P,C)‐ligands obtained as a racemic mixture of the enantiomers RRuSc/SRuRC. These kinetically stable isomers, undergo an isomerization process leading to the thermodynamically stable products isolated as the diastereoisomer RRuRC/SRuSC. 31P{1H} NMR monitoring experiments on the isomerization processes have been carried out.
New Ru complexes containing bidentate κ2(P,C)‐ligands [RuCl(η6‐C10H14){ĸ2(P,C)‐Ph2PCH2CH(PR3)CH2}][BPh4] have been diastereoselectively synthesized as the kinetically stable isomer (RRuSC/SRuRC). This diastereoisomer spontaneously evolves to the thermodynamically stable diastereoisomer (RRuRC/SRuSC). 31P{1H} NMR monitoring experiments shed light on the isomerization processes.