Synthese, Kristallstruktur und fluktuierendes Verhalten von cis‐Cl2Ru(CO)(P∽O)(PˆO) mit cis‐ständigen (Ether‐Phosphan)‐Liganden

Lindner, Ekkehard; Möckel, A.; Mayer, Hermann A.; Fawzi, Riad

doi:10.1002/cber.19921250609

Cited by 15 publications

(2 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Indeed, the Ru(1)−Cl(2) bond (2.4634(8) Å) trans to P(1) is significantly longer than the Ru(1)−Cl(1) bond (2.4420(8) Å) trans to N(1). Moreover, the Ru(1)−O(1) bond trans to P(2) (2.311(2) Å) is one of the longest distances observed for ruthenium complexes with P,O ligands in which the oxygen atom is in a trans position to a phosphorus atom. − This last result suggests that the fluxionality phenomenon observed by NMR for 5b and 6b could result from an easy reversible opening of the Ru−O bond, which is not totally frozen at the lowest temperature we have operated (193 K).…”

Section: Resultsmentioning

confidence: 68%

Ruthenium(II) Complexes Containing Optically Active Hemilabile P,N,O-Tridentate Ligands. Synthesis and Evaluation in Catalytic Asymmetric Transfer Hydrogenation of Acetophenone by Propan-2-ol

et al. 1997

View full text Add to dashboard Cite

The trifunctional ligands (R)-1-(diphenylphosphino)-2-((1R,2S,5R)-menthoxy)-1-(2-pyridyl)ethane (2R), (S)-1-(diphenylphosphino)-2-((1R,2S,5R)-menthoxy)-1-(2-pyridyl)ethane (2S), and (S)-(phenyl(2-anisyl)phosphino)(2-pyridyl)methane (3) have been synthesized, as well as the corresponding RuCl2(PPh3)(L) complexes. The complexes RuCl2(PPh3)(2R) (5) and RuCl2(PPh3)(2S) (6) were isolated as mixtures of two isomers, 5a and 5b and 6a and 6b, respectively. In each of these isomers, the ligands 2 are η3-(P,N,O) bound. They differ by the position of the triphenylphosphine, which is either in a trans position relative to the pyridyl ring (5a or 6a) or in a trans position relative to the ether function (5b or 6b). Variable temperature NMR experiments have shown that the hemilabile character in solution of the ligands 2 is through their pyridyl arm in the isomers a or their ether arm in b. The complexes 6b and RuCl2(PPh3)(3) (9) were characterized by X-ray diffraction. The complexes 5, 6, and 9 are very active catalysts for the transfer hydrogenation of acetophenone by propan-2-ol in basic media, the higher activity being observed for 9 (turnovers frequency 48 900 h-1). The enantioselectivity is modest and dependent on the reactions conditions. The best result has been observed for 5, with an ee of 60%.

show abstract

Section: Resultsmentioning

confidence: 68%

Ruthenium(II) Complexes Containing Optically Active Hemilabile P,N,O-Tridentate Ligands. Synthesis and Evaluation in Catalytic Asymmetric Transfer Hydrogenation of Acetophenone by Propan-2-ol

et al. 1997

View full text Add to dashboard Cite

show abstract

“…The structures of 10 and 11 (Scheme 4) are assigned based on the IR and 31 P NMR spectral data for those compounds. By comparison to the number and position of the bands in the far-IR spectra of related complexes, 42 the RuCl 2 stretching frequencies indicate that the chloro group are trans in 10 and cis in 11. The coupling constants (J PP ) in the 31 P NMR spectra show that the phosphorus atoms in both complexes are in a meridional arrangement around the metal.…”

Section: Reactions Of 8 and 9 With Comentioning

confidence: 99%

Synthesis and reactivity of ruthenium(II) complexes containing hemilabile phosphine–thiophene ligands

Clot

Wolf

Yap

et al. 2000

J. Chem. Soc., Dalton Trans.

View full text Add to dashboard Cite

New Octahedral RuCl2(CO)(L)[η2-(P,O)-ketophosphane] Complexes Containing One Hemilabile Ketophosphane Ligand

Demerseman

2001

Eur. J. Inorg. Chem.

View full text Add to dashboard Cite

The reaction of the ketophosphanes Ph2PCH2C(=O)tBu (1), Ph2PCMe2C(=O)iPr (1′), or Ph2PCMe2CH2C(=O)Me (1′′) with a precursor complex RuCl2(L)(η6‐p‐cymene) [L = PMe3 (a), PMePh2 (b), PiPrPh2 (c), PPh3 (d), P(OMe)Ph2 (e), P(OMe)3 (f)] in methanol and under carbon monoxide, provides an access to a novel family of complexes (ttt)‐RuCl2(CO)(L)[η2‐(P,O)‐ketophosphane] (2a−e, 2′a,e,f, and 2′′a) with trans‐chlorine and trans‐phosphorus atoms. Further reaction with carbon monoxide or acetonitrile under thermal activation yields the cis,cis,trans derivatives (cct)‐RuCl2(CO)2(L)[η1‐(P)‐ketophosphane] 4a,b and 4′a, and (cct)‐RuCl2(CO)(MeCN)(L)[η1‐(P)‐ketophosphane] 5a,b,d. Complexes 2a,b and 2′a rearrange under thermal activation, or after exposure to sunlight, into the (ctc and ccc)‐RuCl2(CO)(L)[η2‐(P,O)‐ketophosphane] isomers, with cis‐chlorine and cis‐phosphorus atoms, 6a,b and 6′a, respectively. Complexes 6a,b reversibly add one molecule of carbon monoxide when forming the all‐cis derivatives (ccc)‐RuCl2(CO)2(L)[η1‐(P)‐ketophosphane] 7a,b, respectively. The removal of one chloride ligand in complexes 4a, 4′a, or 5a with silver tetrafluoroborate affords the stable cationic derivatives {RuCl(CO)(L′)(PMe3)[η2‐(P,O)‐ketophosphane]}[BF4], 8a and 8′a (L′ = CO) and 9a (L′ = MeCN), respectively. Mild basic conditions are sufficient to allow the synthesis of the enolatophosphane derivatives (ttt)‐RuCl(CO)2(L)[η2‐(P,O)‐Ph2PCH=C(tBu)O], 10a,c,e, and of the analogous (ccc) and (cct) isomers, 11a,b and 12a, respectively.

show abstract

Synthese, Kristallstruktur und fluktuierendes Verhalten von cis‐Cl₂Ru(CO)(P∽O)(PˆO) mit cis‐ständigen (Ether‐Phosphan)‐Liganden

Cited by 15 publications

References 15 publications

Ruthenium(II) Complexes Containing Optically Active Hemilabile P,N,O-Tridentate Ligands. Synthesis and Evaluation in Catalytic Asymmetric Transfer Hydrogenation of Acetophenone by Propan-2-ol

Ruthenium(II) Complexes Containing Optically Active Hemilabile P,N,O-Tridentate Ligands. Synthesis and Evaluation in Catalytic Asymmetric Transfer Hydrogenation of Acetophenone by Propan-2-ol

Synthesis and reactivity of ruthenium(II) complexes containing hemilabile phosphine–thiophene ligands

New Octahedral RuCl2(CO)(L)[η2-(P,O)-ketophosphane] Complexes Containing One Hemilabile Ketophosphane Ligand

Contact Info

Product

Resources

About