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

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.

Organoruthenium Complexes Containing Hemilabile Phosphinodicarboxamide Ligands

“…In the particular case of the structures of 4 and 5, the core of the PDCA ligands is twisted compared to the free ligand, 9 which most likely arises from π•••π stacking interactions between an aminic aryl group and the phenyl phosphine fragment, and highlights the conformational flexibility of the PDCA ligand [C17plane-C24plane = 3.635(3) Å (4); C23plane-C9plane = 3.540(2) Å ( 5)]. The Ru-Cl and Ru-P distances for 1-5 (Table 2), are similar to related phosphorus-bound ruthenium compounds, 2,15,16,24,25,30 such as [Ru(p-cym){PH2(CO)NHCy}Cl2] and [Ru(p-cym){PPh2C≡CPh}Cl2] (Ru-Cl; ≈ 2.40 Å , Ru-P; ≈ 2.35 Å). 2,24 In addition, complexes 1-5 present intramolecular hydrogen bonding between the amidic proton and one of the metal-bound chlorides in the solid-state.…”

Organoruthenium Complexes Containing Phosphinodicarboxamide Ligands

“…In the particular case of the structures of 4 and 5, the core of the PDCA ligands is twisted compared to the free ligand, [9] which most likely arises from π• • • π stacking interactions between an aminic aryl group and the phenyl phosphine fragment, and highlights the conformational flexibility of the PDCA ligand [C17plane -C24plane = 3.545(2) Å (4); C23 plane -C9 plane = 3.540(2) Å ( 5)]. The Ru-Cl and Ru-P distances for 1-5 (Table 2), are similar to related phosphorus-bound ruthenium compounds [2,15,16,24,25,30] such as [Ru(p-cym){PH 2 (CO)NHCy}Cl 2 ] and [Ru(pcym){PPh 2 C≡CPh}Cl 2 ] (Ru-Cl; ≈ 2.40 Å, Ru-P; ≈ 2.35 Å) [2,24]. In the case of the crystal structure determinations for 1, 4 and 5, additional interstitial molecules of solvent were found (C 6 H 6 and toluene, respectively) and could be sensibly modelled.…”