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Volumn 46, Issue 25, 2007, Pages 10479-10490

Mononuclear Rh(II) PNP-type complexes. Structure and reactivity

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EID: 37349116216     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic701044b     Document Type: Article
Times cited : (65)

References (79)
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    • For reviews on mononuclear rhodium (II) complexes see (a) de Bruin, B.; Hetterscheid, D. G. H. Eur. J. Inorg. Chem. 2007, 211-230.
    • For reviews on mononuclear rhodium (II) complexes see (a) de Bruin, B.; Hetterscheid, D. G. H. Eur. J. Inorg. Chem. 2007, 211-230.
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    • For recent examples, see a
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    • For example, activation of various substrates by (TMP)Rh(II) (a) dihydrogen: Wayland, B. B.; Ba, S.; Sherry, A. E. Inorg. Chem. 1992, 31, 148-150.
    • For example, activation of various substrates by (TMP)Rh(II) (a) dihydrogen: Wayland, B. B.; Ba, S.; Sherry, A. E. Inorg. Chem. 1992, 31, 148-150.
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    • methane: Wayland, B. B.; Ba, S.; Sherry, A. E. J. Am. Chem. Soc. 1991, 113, 5305-5311.
    • (b) methane: Wayland, B. B.; Ba, S.; Sherry, A. E. J. Am. Chem. Soc. 1991, 113, 5305-5311.
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    • ethane and CO: Cui, W.; Li, S.; Wayland, B. B. J. Organomet. Chem. 2007, 692, 3198-3206.
    • (c) ethane and CO: Cui, W.; Li, S.; Wayland, B. B. J. Organomet. Chem. 2007, 692, 3198-3206.
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    • (b) Szabó, K. J. Synlett 2006, 6, 811-824.
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    • For examples of stabilization by π donation of chloride see (a) Riehl, J. F, Jean, Y, Eisenstein, O, Pélissier, M. Organometallics 1992, 11, 729-737
    • For examples of stabilization by π donation of chloride see (a) Riehl, J. F.; Jean, Y.; Eisenstein, O.; Pélissier, M. Organometallics 1992, 11, 729-737.
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    • Pseudopotential radii are calculated radii derived from first principles, which can be used for predicting structure and compound formation. International Tables For Crystallography, Kluwer Academic Publishers: Norwell, MA, 1992; C, p 682.
    • Pseudopotential radii are calculated radii derived from first principles, which can be used for predicting structure and compound formation. International Tables For Crystallography, Kluwer Academic Publishers: Norwell, MA, 1992; Vol. C, p 682.
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    • 4] (ref 9).
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    • 3H][OTf], formed by the addition of triflic acid to an acetone solution of triethylphosphine, gave a signal at 44.41 ppm.
    • 3H][OTf], formed by the addition of triflic acid to an acetone solution of triethylphosphine, gave a signal at 44.41 ppm.
  • 72
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    • The presence of the non-coordinating BArf is significant in this reaction. Reaction of 4, 6 and, PNPtBu)RhCl, BArf] with CO gave exclusively 13, whereas the reaction of, PNP tBu)RhCl][BF4] with CO afforded 13 as a major product (75% yield according to 31P NMR) along with a new complex. Moreover, 4 and 6 react with one equiv of CO, whereas the reaction of 2 with CO required an excess for completion. The new complex exhibits, in the 31P{1H} NMR spectrum, a doublet at 54.4 ppm (JRhP, 84.5 Hz) and in the 19F NMR spectrum a broad signal at -149 ppm (coordinated BF4, This complex is transformed to 13 with time under CO. We assume that the complex is, PNPtBu)Rh(Cl)2BF4
    • 4)].
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    • The X-ray diffraction of 13 was collected at 17°C because at lower temperature the crystals cracked.
    • The X-ray diffraction of 13 was collected at 17°C because at lower temperature the crystals cracked.
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    • For recent mechanistic studies see
    • For recent mechanistic studies see Zhang, L.; Fung, C. W.; Chan, K. S. Organometallics 2006, 25, 5381-89.
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    • Zhang, L.1    Fung, C.W.2    Chan, K.S.3
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    • In the case of added PEt3, the resulting deprotonation process masks the difference in redox reactivity between 2 and 6
    • 3, the resulting deprotonation process masks the difference in redox reactivity between 2 and 6.


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