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Volumn 26, Issue 3, 2007, Pages 586-593

Mechanistic studies on the formation of η2-diphosphine (η6-p-cymene)ruthenium(II) compounds

Author keywords

[No Author keywords available]

Indexed keywords

AMINES; IONIZATION; MASS SPECTROMETRY; RUTHENIUM COMPOUNDS; SUBSTITUTION REACTIONS; ULTRAVIOLET SPECTROSCOPY;

EID: 33847188871     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om060752n     Document Type: Article
Times cited : (39)

References (58)
  • 3
    • 0000426539 scopus 로고
    • Abel, E. W, Stone, F. G. A, Wilkinson, G, Eds, Elsevier; Oxford
    • (c) Bennett, M. A. Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Elsevier; Oxford, 1995, Vol. 7, pp 549-602.
    • (1995) Comprehensive Organometallic Chemistry II , vol.7 , pp. 549-602
    • Bennett, M.A.1
  • 7
    • 0141447358 scopus 로고    scopus 로고
    • Int. Ed, and references therein
    • (g) Castarlenas, R.; Dixneuf, P. H. Angew. Chem., Int. Ed. 2003, 42, 4524-4527, and references therein,
    • (2003) Angew. Chem , vol.42 , pp. 4524-4527
    • Castarlenas, R.1    Dixneuf, P.H.2
  • 11
    • 0002123299 scopus 로고    scopus 로고
    • For illustrative examples see: a
    • For illustrative examples see: (a) Noyori, R.; Hashiguchi, S. Acc. Chem. Res. 1997, 30, 97-102.
    • (1997) Acc. Chem. Res , vol.30 , pp. 97-102
    • Noyori, R.1    Hashiguchi, S.2
  • 26
    • 33847237944 scopus 로고    scopus 로고
    • Abbreviations used for diphosphines and related ligands: PPh 2CH2-PPh2 (dppm, cis-PPh 2CHCHPPh2 (dppv, PPh2(CH2) 2PPh2 (dppe, PPh2-(CH2) 3PPh2 (dppp, 1,1′-bis(diphenylphosphino)ferrocene (dppf, S)-2-(dimethylamino)-3-phenylpropyl]diphenylphosphine S-phephos
    • 2 (dppp), 1,1′-bis(diphenylphosphino)ferrocene (dppf), [(S)-2-(dimethylamino)-3-phenylpropyl]diphenylphosphine (S-phephos).
  • 30
    • 33847175112 scopus 로고    scopus 로고
    • 6, the coordinated phosphorus resonances are non-first-order and are instead observed as a multiplet between 22.0 and 23.7 ppm; see Figure SI.
    • 6, the coordinated phosphorus resonances are non-first-order and are instead observed as a multiplet between 22.0 and 23.7 ppm; see Figure SI.
  • 32
    • 33847181151 scopus 로고    scopus 로고
    • Considerable shifts to higher frequency are observed for the C 4 resonance (see Scheme 1 for labeling) on substitution of the CH3CN, indicative of weaker coordination of C4 to the metal center due to increased steric bulk in the coordination sphere. The increase in steric bulk is also apparent from changes in the p-cymene H 7 and H8 resonances and the H9 and H 10 resonances, which become distinctly diastereotopic for [2a-e]PF6, particularly for [2b]PF6 and [2e]PF6. In the case of [2e]PF6, the observation of a NOE interaction between H6 and H12 Experimental Section, Figure 6, indicating that the dppf ligand adopts a conformation with the ferrocene moiety approaching the plane of the coordinated arene, may help explain the origin of these shifts
    • 12 (Experimental Section, Figure 6), indicating that the dppf ligand adopts a conformation with the ferrocene moiety approaching the plane of the coordinated arene, may help explain the origin of these shifts.
  • 40
    • 33847194464 scopus 로고    scopus 로고
    • The overall of activation is comprised of both intrinsic and solvational contributions (ΔV‡obs, ΔV‡ intr, ΔV‡solv, Because the chelation of 4a and 4b involves the creation of charged species, 5a, Cl, 5b]+Cl, respectively, the overall of activation value will include a negative contribution from changes in the solvation during this process electrostriction, making the precise interpretation of the overall of activation less straightforward [van Eldik, R, Hubbard, C. D. High Pressure Chemistry; van Eldik, R, Klärner, F.-G, Eds, Wiley-VCH: Weinhein, 2002, However, owing to the similarity of these two complexes, contributions from electrostriction are likely to be similar. In addition to the of activation, similar arguments apply to the interpretation of the activation entropies for the chelation of
    • 6, as there is no change in charge, and furthermore 1,2-dichloroethane is an apolar solvent (electrostriction during the chelation of 4b in 1,2-dichloroethane could also be expected to be small).
  • 41
    • 33847199599 scopus 로고    scopus 로고
    • 31P{1H} NMR (CH2ClCH2Cl, internal D2O reference, δ 38.8 (t, 2J pp, 34, 1P, PPh3, 5.6 (dd, 2J pp, 69, 2Jpp, 34, 1P, PPh 2, 4.7 (dd, 2Jpp, 69, 2JPP, 34, 1P, P′Ph2, The analogous compounds [RuCl2(PPh3)(η2-(P-P, P-P, dppp, dppb) have been reported and exhibit similar 31P NMR spectra, although with larger J(P-p)(p-P) coupling constants [ref 18
    • (P-p)(p-P) coupling constants [ref 18],
  • 42
    • 33847215723 scopus 로고    scopus 로고
    • 6, and neutral, 4b, pendant complexes is likely to be reliable. Hence, the large difference in magnitude and different sign of the ΔS‡ values for these complexes supports the mechanistic hypotheses.
    • 6, and neutral, 4b, pendant complexes is likely to be reliable. Hence, the large difference in magnitude and different sign of the ΔS‡ values for these complexes supports the mechanistic hypotheses.
  • 49
    • 34248375032 scopus 로고    scopus 로고
    • Institut des Sciences et Ingénierie Chimiques, EPFL Lausanne
    • Helm, L.; Borel, A.; Yerly, F. NMRICMA 3.0 for Matlab; Institut des Sciences et Ingénierie Chimiques, EPFL Lausanne, 2004.
    • (2004) NMRICMA 3.0 for Matlab
    • Helm, L.1    Borel, A.2    Yerly, F.3
  • 52
    • 33847234179 scopus 로고    scopus 로고
    • Origin 7.0 or
    • OriginLab Corporation: Northampton, MA
    • Origin 7.0 or OriginPro 7.5; OriginLab Corporation: Northampton, MA, 2002.
    • (2002) OriginPro 7.5
  • 54
    • 33847217851 scopus 로고    scopus 로고
    • Bruker AXS, Inc.: Madison, WI, 1997.
    • Bruker AXS, Inc.: Madison, WI, 1997.
  • 57
    • 0004150157 scopus 로고    scopus 로고
    • University of Göttingen: Germany
    • Sheldrick, G. M. SHELXTL; University of Göttingen: Germany, 1997.
    • (1997) SHELXTL
    • Sheldrick, G.M.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.