190195-14-3Relevant academic research and scientific papers
C-C bond formation via C-H bond activation using an in situ-generated ruthenium catalyst
Martinez, Remi,Simon, Marc-Olivier,Chevalier, Reynald,Pautigny, Cyrielle,Genet, Jean-Pierre,Darses, Sylvain
, p. 7887 - 7895 (2009/10/17)
We report here our full results concerning the possibility of generatingin situ from a stable and readily available ruthenium(II) source a high ly active ruthenium catalyst for C-H bond activation. The versatility ofthis catalytic system has been demonstrated, as it offers the possibili ty of modifying the electronic and steric properties of the catalyst by fine-tuning of the ligands, allowing functionalization of various substrates. Aromatic ketones and imines could be easily functionalized by the reaction with either vinylsilanes or styrenes, depending on the electronic and steric nature of the ligand. Moreover, variable-temperature NMR experiments and the isolation of a ruthenium intermediate complex provided some insights into the generation of the active catalytic ruthenium species in this reaction.
Synthesis and characterisation of [(η6-cymene)Ru(L)X 2] compounds: Single crystal X-ray structure of [(η6- cymene)Ru(P{OPh}3)Cl2] at 203 K
Hodson, Emma,Simpson, Stephen J.
, p. 2695 - 2707 (2008/10/09)
Treatment of the chloro bridged dimer {[(η6-cymene)RuCl] 2(μ-Cl)2} (1) with the donor molecules in hot hexane causes bridge splitting reactions that produce the monomeric compounds [(η6-cymene)Ru(L)Cl2]. Treatment of the chloro bridged dimer {[(η6-cymene)RuCl]2(μ-Cl)2} (1) with the donor molecules P(OPh)3, P(OMe)3, PPh 3, PMe3, CO, SMe2, CNtBu and CNTos in hot hexane causes bridge splitting reactions that produce the monomeric compounds [(η6-cymene)Ru(L)Cl2], (4)-(11), respectively. Use of the chiral isonitrile S(-)-α-methylbenzylisonitrile produced the corresponding complex 12. The diiodo analogues, 13-15, were prepared similarly from {[(η6-cymene)RuI]2(μ-I) 2} (3) for P(OPh)3, P(OMe)3 and PPh 3, respectively. Insertion of tin(II) chloride into both metal-chlorine bonds was observed for [(η6-cymene)Ru(P{OMe} 3)Cl2] (5), while only monosubstitution was observed for [(η6-cymene)Ru(PPh3)Cl2] (6). Halide abstraction in the presence of a substrate reaction has been used to prepare some selected cationic compounds which contain an asymmetric ligand environment. Reaction of {[(η6-cymene)RuCl]2(μ-Cl)2} with 1,2-bis(diphenylphosphino)-ethane under ionising conditions produced the cation [(η6-cymene)Ru(dppe)Cl]PF6 (20). Selected compounds have been examined by {13C-1H} heteronuclear correlation and {1H-1H} COSY and NOESY experiments. The structure of [(η6-cymene)Ru(P{OPh}3)Cl2] ? CH2Cl2 (4) has been determined at -70°C.
