A ruthenium(II) complex withp-cymene and (S)-2-(anilinomethyl)pyrrolidine

Abstract

The title compound, [(S)-2-(anilinomethyl)pyrrolidine-N, N']-chloro(eta(6)-para-cymene)ruthenium(II) chloride, [RuCl-(C(10)H(14))(C(11)H(16)N(2))]Cl, has been synthesized by the reaction of [RuCl(2)(p-cymene)](2) (p-cymene is para-isopropyltoluene) with (S)-2-(anilinomethyl)pyrrolidine in triethylamine/2-propanol. The Ru atom is in a pseudo-tetrahedral environment coordinated by a chloride ligand, the aromatic hydrocarbon is linked in a eta(6) manner and the amine is linked via its two N atoms. The chloride anion is involved in hydrogen bonding with the diamine moieties through N-H.Cl interactions, with N.Cl distances of 3.273 (4) and 3.352 (4) A.

Chloro(η6-p-cymene)[(1R)-(+)-3-(4-methoxybenzoyl)camphor(1–)-κ2O,O′]ruthenium(II)

“…The Ru-Cl distance is slightly short compared with the distance [2.4199 (6) Å ] found in the reported Rh I complex (Aitali et al, 2000). The coordination environment yields a chiral ruthenium center with the S configuration (Stanley & Baird, 1975).…”

“…The use of a 1,3-diketone as ligand has found applications in, for example, hydrogenation (Brunner & Wagenhuber, 1996), hydroformylation (Mieczynska et al, 1999) oxidation (Fdil et al, 1996;Mastrorilly et al, 2001) and hetero Diels-Alder reactions (Togni et al, 1993). With this background, we have reported the structure of a monomeric rhodium(I) complex, [Rh(1R)-(+)-3-benzoylcamphoryl] [Rh(cycloocta-1,5-diene)] (Spannenberg et al, 2002), as well as a ruthenium(II) complex, [(S)-2-(anilinomethyl)pyrrolidine-N,N 0 ]-chloro(p-cymene)Ru] (Aitali et al, 2000). Often, and despite its successful activity, reliable information about the nature of the active species and its chemical interaction with the substrate is not available.…”

Transfer hydrogenation reactions catalyzed by chiral half-sandwich Ruthenium complexes derived from Proline

“…Metal complexes were synthesized by carrying out the reaction of ruthenium cymene dimer with chiral (S)-N-substituted 2-aminomethylpyrrolidine ligands (Scheme 4). 40 The corresponding chiral ruthenium complexes C1, C2, C3 and C4 were obtained as yellow crystalline complexes whose structures were confirmed by NMR, ESI-HRMS and X-ray crystallography.…”

4-Chloro-N-methyl-2-(1,2,3,4-tetrahydroisoquinolin-1-yl)aniline

“…For the use of diamine ligands in enantioselective hydrogenation of ketones, see: Xie et al (2009); Morilla et al (2007); Aitali et al (1995Aitali et al ( , 2000a; Ohkuma et al (1995). For related structures, see: Aitali et al (2000b); Nakahara et al (1998); Suna (2003); Vedejs et al (1999). Mo K radiation = 0.27 mm À1 T = 100 K 0.57 Â 0.54 Â 0.34 mm…”

“…N-methyl-2-(1,2,3,4- We have been focusing our research on the use of diamines which can lead to the synthesis of chiral metal complexes with application, for example, as catalysts in asymmetric hydrogenation processes (Xie et al, 2009;Ohkuma et al, 1995); in the asymmetric transfer hydrogenation (Aitali et al, 2000a;Morilla et al, 2007;Aitali et al, 1995). As part of our study, we came across (-)-1-[5-chloro-2-(methylamino)-phenyl]-1,2,3-4-tetrahydro-isoquinolin, an interesting chiral diamine capable of forming chelates with transition metal centres (Aitali et al, 2000b). Here we report the crystal structure of a racemic melange containing R and S diamine forms (S.G. C2/c) .…”