Half‐Sandwich η⁵‐Indenyl‐ and η⁶‐Areneruthenium(II) Complexes Bearing the Chiral Ligand (4S)‐2‐[(S_p)‐2‐(Diphenylphosphanyl)ferrocenyl]‐4‐(methylethyl)oxazoline (FcPN)

Abstract

Chiral indenylruthenium(II) [Ru(η5‐C9H7){κ2(P,N)‐FcPN}(PPh3)][PF6] (1), [Ru(η5‐C9H7)Cl{κ2(P,N)‐FcPN}] (2) and areneruthenium(II) [RuX(η6‐arene){κ2(P,N)‐FcPN}][PF6] [η6‐arene = p‐cymene, X = Cl (6a), H (7), N3 (8); η6‐arene = 1,2,3,4‐tetramethylbenzene, X = Cl (6b)] complexes containing the chiral ligand (4S)‐2‐[(SP)‐2‐(diphenylphosphanyl)ferrocenyl]‐4‐(methylethyl)oxazoline (FcPN) have been synthesised diastereoselectively. Reaction of 2 with terminal alkynes allows the synthesis of alkynyl [Ru(η5‐C9H7)(C≡CR){κ2(P,N)‐FcPN}] [R = Ph (3a), p‐CH3C6H4 (3b)], allenylidene [Ru(η5‐C9H7){κ2(P,N)‐FcPN}(=C=C=CPh2)][PF6] (4) and Fischer‐type carbene [Ru(η5‐C9H7){κ2(P,N)‐FcPN}{=C(OMe)CH=CHPh}][PF6] (5) complexes. The structures of complexes 2, 3a and 6a have been determined by X‐ray diffraction methods. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

The Stereospecific Ligand Exchange at a Pseudo‐Benzylic T‐4 Iridium Centre in Planar‐Chiral Cycloiridium (η6‐Arene)tricarbonylchromium Complexes

“…[10][11][12][13] If a restriction to the rearrangement of a ligand can be imposed, control of the facial approach of the metal by the incoming ligand can be achieved. [14][15][16][17][18] This may be realised with appended auxiliary ligands capable of reversibly binding the metal centre and constraining the ligand-exchange process to fewer stereochemical paths than in an unconAbstract: The stereospecificity of ligand exchange at the Ir III centre of a cycloiridium arenetricarbonylchromium complex has been established experimentally by various analytical methods as well as by X-ray diffraction structural analysis and computational investigations. Two new cases of phenyl and methyl iridiumA C H T U N G T R E N N U N G (III) complexes have been prepared by reaction of (S* p ,R* Ir )-chlorido{2-[(tricarbonyl)(h 6 -phenylenekC 1' )chromium(0)]pyridinekN}(pentamethylcyclopentadienyl)iridiumA C H T U N G T R E N N U N G (III) with PhMgBr and MeMgBr.…”

Asymmetric transfer hydrogenation of ketones catalyzed by ruthenium(II) complexes bearing a chiral phosphinoferrocenyloxazoline ligand

“…The catalytic activity of these complexes in asymmetric transfer hydrogenation of ketones along with that of six-coordinate 1-3 and half-sandwich 4-8 ruthenium(II) complexes previously reported by us [8,9], is also described.…”

“…2): (a) six-coordinate complexes [8] of general formula [RuCl 2 L 2 {j 2 -(P,N)-FcPN}] (L = PMe 3 (1), PMe 2 Ph (2), dppm (3)) and (b) chiral at metal g 5 -indenyl and g 6 -arene ruthenium(II) complexes [Ru(g 5 -C 9 H 7 )(PPh 3 ){j 2 (P,N)-FcPN}][PF 6 ] (4), [RuCl(g 5 -C 9 H 7 ){j 2 (P,N)-FcPN}] (5) and [RuX(g 6 -arene){j 2 (P,N)-FcPN}] [PF 6 ] (X = Cl (6), H (7); arene = p-cymene, 1,2,3,4-tetramethylbencene (8)) which have been isolated as single diastereoisomers (S Ru for g 5 -indenyl complexes and R Ru for g 6 -arene complexes) [9].…”

“…Herein, we describe the synthesis of new six-coordinate ruthenium(II) complexes mer-trans-[RuCl 2 {P(OMe) 3 } 2 {j 2 (P,N)-FcPN}] (9), mer-trans-[RuCl 2 (PTA) 2 {j 2 (P,N)-FcPN}] (10a) and fac-[RuCl 2 (P-TA) 2 {j 2 (P,N)-FcPN}] (10b) (PTA = 1,3,5-triaza-7-phosphadamantane). The catalytic activity of these complexes in asymmetric transfer hydrogenation of ketones along with that of six-coordinate 1-3 and half-sandwich 4-8 ruthenium(II) complexes previously reported by us [8,9], is also described.…”

1,2‐P,N‐Bidentate Ferrocenyl Ligands

“…The catalytic activity of these complexes in the asymmetric transfer hydrogenation of ketones along with that of sixcoordinate (Table 5.5, entries 1-3) and half-sandwich (Table 5.5, entries 4-7 Ru(II) complexes was also described [26,27]. Table 5.5 shows the catalytic activity of the studied complexes in asymmetric transfer hydrogenation.…”