Chloro(η5-dihydropentalenyl)bis(triphenylphosphine)ruthenium(II): synthesis, structural characterization and catalytic activity in the dimerization of phenylacetylene

pH-Dependent Selective Transfer Hydrogenation of α,β-Unsaturated Carbonyls in Aqueous Media Utilizing Half-Sandwich Ruthenium(II) Complexes

“…This suggests that Cp* and Dp ligands may have similar stereoelectronic influence on the metal center. The Ru−P (2.264, 2.257 Å), Ru−Cl (2.452 Å), and Ru−Cp cent (1.855 Å) distances for 4 are comparable to those of the Cp and Cp* analogues, Table . , The saturated portion of the η 5 -C 8 H 9 (Dp) ligand of 4 has an endo-conformation with an envelope angle of 28.4°, defined as the dihedral angle between the C 5 H 3 plane and that of C18−C19−C20, slightly larger than that reported for DpRu(PPh 3 ) 2 Cl (26.4°) . The envelope angle in DpRu(PTA)(PPh 3 )Cl was found to be 29.5°, larger than that observed for either DpRu(PPh 3 ) 2 Cl or 4 .…”

“…14,16 The saturated portion of the η 5 -C 8 H 9 (Dp) ligand of 4 has an endo-conformation with an envelope angle of 28.4°, defined as the dihedral angle between the C 5 H 3 plane and that of C18-C19-C20, slightly larger than that reported for DpRu(PPh 3 ) 2 Cl (26.4°). 19 The envelope angle in DpRu(PTA)(PPh 3 )Cl was found to be 29.5°, larger than that observed for either DpRu(PPh 3 ) 2 Cl or 4. The (N)C-N distances for the triazacyclohexane ring of the PTA ligands in complexes 1-5 are consistent with nonprotonated PTA ligands (N-C(N) ) 1.447-1.480 Å).…”

“…Tetrakis(hydroxymethyl)phosphonium chloride was obtained from Cytec and used without further purification. DpRu(PPh 3 ) 2 Cl, 19 1,3,5-triaza-7-phosphaadamantane (PTA), 20,21 CpRu(PPh 3 ) 2 Cl, 22 IndRu(PPh 3 ) 2 Cl, 23 and CpRu(PTA) 2 Cl 14,16 were prepared as described in the literature. GC/MS analyses were obtained using a Varian CP 3800 GC (DB5 column) equipped with a Saturn 2200 MS and a CP 8400 auto-injector.…”

Atom Transfer Radical Addition Reactions of CCl4, CHCl3, andp-Tosyl Chloride Catalyzed by Cp′Ru(PPh3)(PR3)Cl Complexes

“…The series of Cp′Ru(PR 3 )(PPh 3 )Cl complexes 1 − 10 (Figure ) have been synthesized in good yields by ligand exchange of the Cp′Ru(PPh 3 ) 2 Cl complexes 11 − 15 with the appropriate PR 3 ligand (PTA or PMe 3 ). The synthesis and characterization of CpRu(PTA)(PPh 3 )Cl, DpRu(PTA)(PPh 3 )Cl, IndRu(PTA)(PPh 3 )Cl, TpRu(PTA)(PPh 3 )Cl, CpRu(PMe 3 )(PPh 3 )Cl, IndRu(PMe 3 )(PPh 3 )Cl, Cp*Ru(PPh 3 ) 2 Cl, DpRu(PPh 3 ) 2 Cl, IndRu(PPh 3 ) 2 Cl, CpRu(PPh 3 ) 2 Cl, and TpRu(PPh 3 ) 2 Cl have been previously reported in the literature. We report here the new compounds Cp*Ru(PTA)(PPh 3 )Cl, Cp*Ru(PMe 3 )(PPh 3 )Cl, DpRu(PMe 3 )(PPh 3 )Cl, and TpRu(PMe 3 )(PPh 3 )Cl, along with the solid-state structure of IndRu(PMe 3 )(PPh 3 )Cl and an alternative synthesis for CpRu(PMe 3 )(PPh 3 )Cl.…”

“…Solvents were dried with molecular sieves and degassed with N 2 , prior to use. Cp*Ru(PPh 3 ) 2 Cl, DpRu(PPh 3 ) 2 Cl, IndRu(PPh 3 ) 2 Cl, CpRu(PPh 3 ) 2 Cl, TpRu(PPh 3 ) 2 Cl, CpRu(PTA)(PPh 3 )Cl, , DpRu(PTA)(PPh 3 )Cl, TpRu(PTA)(PPh 3 )Cl, IndRu(PTA)(PPh 3 )Cl, IndRu(PMe 3 )(PPh 3 )Cl, and 1,3,5-triaza-7-phosphaadamantane (PTA) were prepared as described in the literature. Kharasch reactions were carried out in standard NMR tubes or in 1.5 mL vials.…”