Stabilization of the labile metal configuration in halfsandwich complexes [CpRh(PN)Hal]X

Brunner, Henri; Köllnberger, Andreas; Mehmood, Arshad; Tsuno, Takashi; Zabel, Manfred

doi:10.1016/j.jorganchem.2004.07.057

Cited by 13 publications

(7 citation statements)

References 36 publications

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“…[9a] This latter, lately renamed 6-DPPon has also found wide applications in self assembling system for hydroformylation. [9b] Based on the previous findings of Brunner who demonstrated that chelating Oalkylated phosphine-pyridones could undergo deprotection, [10] we reported the direct access to the corresponding phosphinepyridone for the catalytic hydrogenation of unfunctionalized ketones and for acetal formation from primary alcohols.…”

Section: Introductionmentioning

confidence: 97%

Phosphine-pyridonate ligands containing octahedral ruthenium complexes: access to esters and formic acid

Sahoo

Jiang

Bruneau

et al. 2017

Catal. Sci. Technol.

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Section: Introductionmentioning

confidence: 97%

Phosphine-pyridonate ligands containing octahedral ruthenium complexes: access to esters and formic acid

Sahoo

Jiang

Bruneau

et al. 2017

Catal. Sci. Technol.

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“…All bonds lengths and angles in this structure are within expected range. C21-N1-S2 115.78 (10) C21-N1-H1A 112.51 (14) S2-N1-H1A 109.78 (11) *Ct1 and Ct2 are the centroids of the Cp rings (6,8,10).…”

Section: Ligands Synthesismentioning

confidence: 99%

“…Indeed, reaction of a pure R configurated bidendate ligand (RL) will conduct to two diastereoisomers (RLRM) and (RLSM) and the selective formation of one specific diastereoisomer may be a challenge. 5,6 One family of such chiral-at-metal complexes are the half sandwich complexes of ruthenium, rhodium and iridium, that have found efficient applications for instance in Asymmetric Transfer Hydrogenation (ATH). Ligands used for this reaction are mainly aminoalcohols or bidendate N,N ligands bearing a NH bond which is involved in the hydrogen transfer mechanism according to Noyori's proposal.…”

Section: Introductionmentioning

confidence: 99%

Coordination Chemistry of New Chiral P,N Ferrocenyl Ligands with Half-Sandwich Ruthenium(II), Rhodium(III), and Iridium(III) Complexes

et al. 2012

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New half-sandwich ruthenium(II), rhodium(III) and iridium(III) complexes (p-cymene)RuCl2L and Cp*MCl2L (M = Rh, Ir) where L is a planar chiral ferrocenyl tosylamine-phosphine ligand {1,2-(TosNRCH2)(PPh2)C5H3}FeCp (R = H, Me) coordinated in a monodendate fashion (κ 1 :P) have been synthesized and fully characterized both in solution (multinuclear NMR, mass spectrometry) and in the solid state (X-ray analysis on single crystals). Intra and inter molecular N-H•••Cl bonds were observed. Variable temperature NMR shows equilibrium between different structures which have been discussed with the help of DFT calculations. Addition of triethylamine to the complexes with R = H allows removing the tosylamide acidic hydrogen giving rise to a ferrocenyl amidophosphine ligand coordinated in a bidendate fashion (κ 2 :P,N). All complexes have been fully characterized by multinuclear NMR and mass spectrometry. The structure of the iridium complex, determined by X-ray diffraction, shows a planar nitrogen atom and a stable metal-centered chirality. Only the most stable diastereoisomer, according to DFT calculations has been observed. A number of these complexes were assessed in the catalytic transfer hydrogenation and asymmetric transfer hydrogenation of acetophenone.

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“…For the structural parameters of mono-alkyl substituted cyclopentadienes (organic structures only), see: Tacke et al (2001); Liebling & Marsh (1965); Haumann et al(1996); Deck et al (2004); Malpass et al (2004); Cheung et al (2005); Bauer et al (2001); Huerlander et al (2002); Millelr & Bercaw (2004); Li et al (2005); Brunner et al (2004); Otero et al (2007); Hutton et al (2008). For the structural parameters of 1,2dialkyl-1H-imidazoles (organic structures only, not bi-or oligocyclic, non-ionic), see: Bruijnincx et al (2005); Aakeroy et al (2006); Zhang et al (2007); Upadhyaya et al (1997); Braussaud et al (2001); Peters et al (2005); Laus et al (2008).…”

Section: Related Literaturementioning

confidence: 99%

2-[(Cyclopenta-1,3-dien-2-yl)diphenylmethyl]-1-methyl-1H-imidazole

2010

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The title compound, C22H20N2, (Ib), forms along with 2-[(cyclopenta-1,3-dien-1-yl)diphenylmethyl]-1-methyl-1H-imidazole, (Ia), which differs with respect to the position of the double-bonds in the C5H5 ring, in an approximately 3:7 ratio (Ia:Ib; NMR spectroscopy data). However, in a single crystal, only compound (Ib) is present. H atoms of the CH2 group (C5H5 ring) were found from the difference Fourier synthesis and refined isotropically using the riding model. Hypothesis on possible presence of the (Ia) isomer in crystal lattice (model with a C5H5 ring disordered between two positions) was especially checked and rejected due to its inconsistency. In the crystal structure, no significant hydrogen-bonding interactions between the CH2 groups of the C5H5 rings and nonsubstituted N-atoms of the imidazole rings were observed. Despite the fact that the chemically achiral compound (I) crystallizes in a chiral space group P212121, neither the absolute structure determination nor assignment of the inversion twinning was possible in the absence of a heavy atom.

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Stabilization of the labile metal configuration in halfsandwich complexes [CpRh(PN)Hal]X

Cited by 13 publications

References 36 publications

Phosphine-pyridonate ligands containing octahedral ruthenium complexes: access to esters and formic acid

Phosphine-pyridonate ligands containing octahedral ruthenium complexes: access to esters and formic acid

Coordination Chemistry of New Chiral P,N Ferrocenyl Ligands with Half-Sandwich Ruthenium(II), Rhodium(III), and Iridium(III) Complexes

2-[(Cyclopenta-1,3-dien-2-yl)diphenylmethyl]-1-methyl-1H-imidazole

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