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Volumn 27, Issue 20, 2008, Pages 5180-5183

Generation of α-phosphinocarbene complexes and their evolution: New light on relevant isomerization pathways

Author keywords

[No Author keywords available]

Indexed keywords

ACIDS; DYES; ELECTRON TRANSITIONS; ISOMERIZATION; ISOMERS; MANGANESE COMPOUNDS;

EID: 55249110235     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om800884v     Document Type: Article
Times cited : (14)

References (59)
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    • (b) Topics in Organometallic Chemistry: Dötz, K. H., Ed.; Wiley: New York, 2004; Vol. 13.
    • (2004) Topics in Organometallic Chemistry , vol.13
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    • For metallacyclic complexes containing M=C-PRR′ fragments, see: (a) Jamison, G. M.; Saunders, R. S.; Wheeler, D. R.; Alam, T. M.; McClain, M. D.; Loy, D. A. Organometallics 1996, 15, 3244-3246.
    • For metallacyclic complexes containing M=C-PRR′ fragments, see: (a) Jamison, G. M.; Saunders, R. S.; Wheeler, D. R.; Alam, T. M.; McClain, M. D.; Loy, D. A. Organometallics 1996, 15, 3244-3246.
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    • Despagnet, E. Ph.D. Thesis, Université Paul Sabatier, Toulouse, France, 2002 (national no. 2002TOU30073).
    • (b) Despagnet, E. Ph.D. Thesis, Université Paul Sabatier, Toulouse, France, 2002 (national no. 2002TOU30073).
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    • VCH: Weinheim, Germany
    • (a) Kreissl, F. R. Carbyne Complexes; VCH: Weinheim, Germany, 1988; p 117.
    • (1988) Carbyne Complexes , pp. 117
    • Kreissl, F.R.1
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    • 7b
    • 7b
  • 29
    • 55249124903 scopus 로고    scopus 로고
    • Selected NMR data for 4b: 31P NMR (CD 2Cl2) δ 25.5 (dt, 1JPH, 545.7 Hz, 3JPH, 14 Hz) ppm; 13C{1H} NMR (CD2Cl2) δ 325.2 d, 1JPC, 24.5 Hz, Mn=C, ppm
    • PC = 24.5 Hz, Mn=C)) ppm.
  • 30
    • 0001511425 scopus 로고    scopus 로고
    • For explicit intramolecular insertion of CO across the M=C bond see: (a) Mitsudo, T.; Watanabe, H.; Sasaki, T.; Takegami, Y.; Watanabe, Y.; Kafuku, K.; Nakatsu, K. Organometallics 1989, 8, 368-378.
    • For explicit intramolecular insertion of CO across the M=C bond see: (a) Mitsudo, T.; Watanabe, H.; Sasaki, T.; Takegami, Y.; Watanabe, Y.; Kafuku, K.; Nakatsu, K. Organometallics 1989, 8, 368-378.
  • 32
    • 55249124205 scopus 로고    scopus 로고
    • Selected spectroscopic data for 6c: 1H NMR (300.1 MHz, C6D5CD3, 298 K) δ 6.99 (t, 3JHH, 6.6 Hz, 2H, m-H (Ph, 6.81 (t, 3JHH, 6.6 Hz, 1H, p-H (Ph, 6.80 (d, 1JPH, 260.4 Hz, 1H, PHMes, 6.69 (s, 2H, m-H (Mes, 6.61 (d, 3JHH, 7.3 Hz, 2H, o-H (Ph, 4.49 (s, 5H, C5H5, 2.52 (s, 6H, o-CH3 (Mes, 2.04 (s, 3H, p-CH3 (Mes, ppm; 31P NMR (121.5 MHz, C6D5CD3, 298 K) δ 18.9 (d, 1JPH, 260.4 Hz) ppm; 13C{1H) NMR (125.8 MHz, C6D5CD3, 240 K) δ358.2 (d, 1JPC, 75.5 Hz, Mn=C-P, 233.0 (br s, Mn-CO, 118.2-142.9 (Ph and Mes, 90.5 (s, C5H5, 24.1 (br s, o-CH 3, 20.9 s, p-CH3
    • -1.
  • 33
    • 55249087346 scopus 로고    scopus 로고
    • -3. CCDC-692689 contains full crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre at www.ccdc.cam.ac.uk/data_request/cif.
    • -3. CCDC-692689 contains full crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre at www.ccdc.cam.ac.uk/data_request/cif.
  • 34
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    • -1.
    • -1.
  • 35
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    • -1.
    • -1.
  • 36
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    • Chemical shifts of carbene Cα atoms in L 2ClRh=C(Ar)P(NiPr2)2 (δ 114.4 ppm, L2, CO)2; δ 120.6 ppm, L2, η4-nbd)6a are very upfield compared to shifts for the structurally similar (η4-cod)ClRh=C(OEt)R (δ 291.1 ppm)16b and, η4-cod)(CO)Rh=C(OEt)R, δ 281.2-297.4 ppm).16c Also, the Rh-Cα bond distance in (η4-nbd)ClRh=C(Ar)P(NiPr2) 2 (2.097 Å6a) is longer than the regular Rh=C bond (for example d(Rh-Cα, 1.994 Å in, η4- cod)(CO)Rh=C(OEt)CH=CHC6H4OMe], 16c) and the P-Cα bond (1.637 Å) is significantly shorter than a single bond (dP-C, 1.80-1.82 Å
    • α bond (1.637 Å) is significantly shorter than a single bond (d(P-C) = 1.80-1.82 Å).
  • 39
    • 55249102315 scopus 로고    scopus 로고
    • Selected spectroscopic data for 5c: 31P NMR (THF-d 8, 298 K, δ-44.0 (d, 1JPH, 403.8 Hz) ppm; 13C{1H} NMR (C6D5CD 3, 233 K) δ 239.9 (d, 2JPC= 19 Hz, P-C=C=O, 230.4 (d, 2JPC, 27.5 Hz, Mn-CO, 28.2 (d, 1JPC, 31.5 Hz, P-C=C=O) ppm; IR (THF) 1932 (s, v CO, 1725 (m br, vC=C=O) cm-1
    • -1.
  • 40
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    • -1.
    • -1.
  • 41
    • 37049092356 scopus 로고    scopus 로고
    • Selected data for 7c: -31P NMR (C6D6. 298 K) δ 281.6 (br s) ppm; 13C{1H} NMR (C 6D6, 298 K) δ166.9 (d, 1JPC, 47 Hz, P=C) ppm. Selected data for 7d: 31P NMR (C6D 6, 298 K) δ 278.8 (br s) ppm; 13C{1H} NMR (C6D6, 298 K) δ 161.2 (d, 1J PC, 54.5 Hz, P=C, These data are very similar to those of (η1-P(Mes)=CPh2) transition-metal complexes: Eshtiagh-Hosseini, H, Kroto, H. W, Nixon, J. F, Maah, M. J, Taylor, M. J. J. Chem. Soc, Chem. Commun. 1981, 199-200
    • 2) transition-metal complexes: Eshtiagh-Hosseini, H.; Kroto, H. W.; Nixon, J. F.; Maah, M. J.; Taylor, M. J. J. Chem. Soc., Chem. Commun. 1981, 199-200.
  • 44
    • 0000258814 scopus 로고    scopus 로고
    • The occurrence of three-band patterns in such anionic complexes is ascribed to an interaction of lithium cations with the oxygen atom of a CO group: (a) Ulmer, S. W, Scarstad, P. M, Burlitch, J. M, Hughes, R. E. J. Am. Chem. Soc. 1973, 95, 4469-4471
    • The occurrence of three-band patterns in such anionic complexes is ascribed to an interaction of lithium cations with the oxygen atom of a CO group: (a) Ulmer, S. W.; Scarstad, P. M.; Burlitch, J. M.; Hughes, R. E. J. Am. Chem. Soc. 1973, 95, 4469-4471.
  • 59
    • 55249118755 scopus 로고    scopus 로고
    • The mixture of ketene (5c or 5d) and phosphaalkene (7c or 7d) complexes was observed during the reaction course, giving finally 7c or 7d in more than 97% E selectivity.
    • The mixture of ketene (5c or 5d) and phosphaalkene (7c or 7d) complexes was observed during the reaction course, giving finally 7c or 7d in more than 97% E selectivity.


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