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79957869890
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Monodentate phosphane ligands with electron-donating substituents may form less active hydroformylation catalysts. The reaction requires therefore longer reaction times:
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Monodentate phosphane ligands with electron-donating substituents may form less active hydroformylation catalysts. The reaction requires therefore longer reaction times:
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79957866482
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Except for few examples phosphite complexes are generally more active than their phosphane-based analogues:
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Except for few examples phosphite complexes are generally more active than their phosphane-based analogues:
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Possibly partial disproportionation of the non-coordinated ligand into bis(p-fluorophenyl)phosphane and bis(p-fluorophenyl)phosphanic acid occurred, as we observed when 3 was stored in a solution at room temperature. This may additionally alter the catalytic results.
-
Possibly partial disproportionation of the non-coordinated ligand into bis(p-fluorophenyl)phosphane and bis(p-fluorophenyl)phosphanic acid occurred, as we observed when 3 was stored in a solution at room temperature. This may additionally alter the catalytic results.
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56
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0003868337
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I-catalysts based on phosphane ligands (electron-rich phosphorus) induce high n-regioselectivties in the hydroformylation of 1-octene, but low activities. In contrast, catalysts based on phosphites (electron-rich phosphorus) are more active, but in general n-aldehydes are obtained in lower yield, in, Eds.: P.W.N.M. Van Leeuwen, C. Claver), Kluwer, Dordrecht, p..
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I-catalysts based on phosphane ligands (electron-rich phosphorus) induce high n-regioselectivties in the hydroformylation of 1-octene, but low activities. In contrast, catalysts based on phosphites (electron-rich phosphorus) are more active, but in general n-aldehydes are obtained in lower yield: P. C. J. Kamer, J. N. H. Reek, P. W. N. M. van Leeuwen in Rhodium Catalyzed Hydroformylation, (Eds.: P.W.N.M. Van Leeuwen, C. Claver), Kluwer, Dordrecht, 2000, p.56.
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In contrast, in related self-assembling Rh-complexes based on H-bridged aminopyridine-isochinolone backbone the selectivities in toluene as well as in MeOH remained the same
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In contrast, in related self-assembling Rh-complexes based on H-bridged aminopyridine-isochinolone backbone the selectivities in toluene as well as in MeOH remained the same: C. Waloch, J. Wieland, M. Keller, B. Breit, Angew. Chem. 2007, 119, 3097-3099
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Kleiner, H.-J.1
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75
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79957823197
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For a review, see
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For a review, see: W. Wolfsberger, Chem. Ztg. 1985, 109, 53-61.
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Chem. Ztg.
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Wolfsberger, W.1
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76
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0034616854
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L. B. Han, F. Mirzaei, C. Q. Zhao, M. Tanaka, J. Am. Chem. Soc. 2000, 122, 5407-5408;
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J. Am. Chem. Soc.
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Han, L.B.1
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77
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33745697845
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N. Ajellal, C. M. Thomas, J. F. Carpentier, Adv. Synth. Catal. 2006, 348, 1093-1100.
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Adv. Synth. Catal.
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Ajellal, N.1
Thomas, C.M.2
Carpentier, J.F.3
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78
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79957862192
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Conditions: 100°C, 22h, THF, Rh/L=1:100, SPO/olefin=1:1.4.
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Conditions: 100°C, 22h, THF, Rh/L=1:100, SPO/olefin=1:1.4.
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79
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11944256836
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C. Casey, G. Whitecker, M. Melville, L. Petrovich, J. Gavney, D. Powell, J. Am. Chem. Soc. 1992, 114, 5535-5543;
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Casey, C.1
Whitecker, G.2
Melville, M.3
Petrovich, L.4
Gavney, J.5
Powell, D.6
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81
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0032544953
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L. A. van der Veen, M. D. K. Boele, F. R. Bregemann, P. C. Kamer, P. W. N. M. Van Leeuwen, K. Goubitz, J. Franje, J. Schenk, C. Bo, J. Am. Chem. Soc. 1998, 120, 11616-11626;
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J. Am. Chem. Soc.
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van der Veen, L.A.1
Boele, M.D.K.2
Bregemann, F.R.3
Kamer, P.C.4
Van Leeuwen, P.W.N.M.5
Goubitz, K.6
Franje, J.7
Schenk, J.8
Bo, C.9
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82
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43949146346
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E. Zuidema, L. Escorihuela, T. Eichelsheim, J. J. Carbó, C. Bo, P. C. J. Kamer, P. W. N. M. Van Leeuwen, Chem. Eur. J. 2008, 14, 1843-1853.
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Chem. Eur. J.
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Zuidema, E.1
Escorihuela, L.2
Eichelsheim, T.3
Carbó, J.J.4
Bo, C.5
Kamer, P.C.J.6
Van Leeuwen, P.W.N.M.7
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83
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0023389515
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W. R. Moser, C. J. Papite, D. A. Brannon, R. A. Duwell, S. J. Weininger, J. Mol. Catal. 1987, 41, 271-292.
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J. Mol. Catal.
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Moser, W.R.1
Papite, C.J.2
Brannon, D.A.3
Duwell, R.A.4
Weininger, S.J.5
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84
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79957831545
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HASPO: O,O'-3,3'-Di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diylphosphonat e. A. Christiansen, D. Selent, A. Spannenberg, M. Köckerling, H. Reinke, W. Baumann, R. Franke, A. Börner, manuscript in preparation.
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HASPO: O, O'-3, 3'-Di-tert-butyl-5, 5'-dimethoxy-1, 1'-biphenyl-2, 2'-diylphosphonate. A. Christiansen, D. Selent, A. Spannenberg, M. Köckerling, H. Reinke, W. Baumann, R. Franke, A. Börner, manuscript in preparation.
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85
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79957836263
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The B3LYP/LANL2DZ level of theory gives too low wavenumbers. Although the LANL2DZ basis set takes relativistic effects for the Rh atom into account, it is certainly not suitable to calculate the absolute frequencies correctly. However, the relative order of the vibrational frequencies is given properly and thus can be used to support the experimental spectra.
-
The B3LYP/LANL2DZ level of theory gives too low wavenumbers. Although the LANL2DZ basis set takes relativistic effects for the Rh atom into account, it is certainly not suitable to calculate the absolute frequencies correctly. However, the relative order of the vibrational frequencies is given properly and thus can be used to support the experimental spectra.
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86
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79957861712
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The nonlinear behavior of the curve can be explained by the measurement principle applied. A part of the solution with the complex 9 was directly transferred into the spectrometer, without prior mixing with toluene in the autoclave. The erratic gradient becomes smaller after every addition since the ratio of the added complex to the reactor solution decreases. After a few minutes a complete mixing is achieved.
-
The nonlinear behavior of the curve can be explained by the measurement principle applied. A part of the solution with the complex 9 was directly transferred into the spectrometer, without prior mixing with toluene in the autoclave. The erratic gradient becomes smaller after every addition since the ratio of the added complex to the reactor solution decreases. After a few minutes a complete mixing is achieved.
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87
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53849113294
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As compared to literature data
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As compared to literature data: C. Li, E. Widjaja, W. Chew, M. Garland, Angew. Chem. 2002, 114, 3939-3943; Angew. Chem. Int. Ed. 2002, 41, 3785-3789.
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Angew. Chem.
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Li, C.1
Widjaja, E.2
Chew, W.3
Garland, M.4
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88
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0037131468
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Angew. Chem. Int. Ed. 2002, 41, 3785-3789
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(2002)
Angew. Chem. Int. Ed.
, vol.41
, pp. 3785-3789
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89
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79957819483
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2) for the main product (ca.85%) a broad doublet was found (75.1ppm, J=964Hz), which probably characterizes a trans Rh complex. The change of the solubility properties may be attributed to the formation of associated 14-electron Rh complexes, which result from the cleavage of the hydrogen bonding connecting both SPO ligands, when CO dissociates from the metal center after release of the syngas pressure.
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2) for the main product (ca.85%) a broad doublet was found (75.1ppm, J=964Hz), which probably characterizes a trans Rh complex. The change of the solubility properties may be attributed to the formation of associated 14-electron Rh complexes, which result from the cleavage of the hydrogen bonding connecting both SPO ligands, when CO dissociates from the metal center after release of the syngas pressure.
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90
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28844439216
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F. Gao, K. P. Ng, K. I. Krummel, A. D. Allian, M. Garland, J. Catal. 2006, 237, 49-57.
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J. Catal.
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Gao, F.1
Ng, K.P.2
Krummel, K.I.3
Allian, A.D.4
Garland, M.5
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91
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0000934330
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W. Chew, E. Widjaja, M. Garland, Organometallics 2002, 21, 1982-1990;
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(2002)
Organometallics
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, pp. 1982-1990
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Chew, W.1
Widjaja, E.2
Garland, M.3
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92
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0001169849
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E. Widjaja, C. Li, M. Garland, Organometallics 2002, 21, 1991-1997;
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Organometallics
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Widjaja, E.1
Li, C.2
Garland, M.3
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