NMR | 薬品分析学 田中研究室

  • Bruker 500 MHz with cryo-BBO probe


  • 資料

    NMR講義資料

    ブルカーNMR導入講習マニュアル


  • データベース

    15N NMR data of N-metallated compounds

    13C NMR data of N-metallated compounds

    13C NMR data of metal-acetylides and a metal-free acetylide


  • 15N NMR data of N-metallated compounds

    Metal-binding
    15N-nuclus
    binding nuclus
    bond
    solvent
    free (ppm)
    bonded (ppm)
    Δ (ppm)
    ref.
    N7(G10.1)
    CdII
    inner-sphere coordination
    H2O
    235.1 (0eq.)
    215.5 (3eq.)
    -19.6
    1-3
    N7(G10.1)
    CdII
    inner-sphere coordination
    H2O
    232.2 (0eq.)
    211.7 (4eq.)
    -20.5
    4
    N7(G10.1)
    ZnII
    inner-sphere coordination
    H2O
    232.2 (0eq.)
    212.2 (4eq.)
    -20.0
    4
    N7(G10.1)
    MgII
    not classified
    H2O
    232.2 (0eq.)
    225.7 (10eq.)
    -6.5
    4
    N7(G10.1)
    Co(NH3)63+
    outer-sphere binding
    H2O
    232.2 (0eq.)
    232.6 (4eq.)
    +0.4
    4
    N7(G)
    Zn(NO3)2
    inner-sphere coordination
    DMSO
    -
    -
    -20.1
    5
    N7(G)
    Hg(NO3)2
    inner-sphere coordination
    DMSO
    -
    -
    -20.5
    5
    N7(I)
    Zn(NO3)2
    inner-sphere coordination
    DMSO
    -
    -
    -15.2
    6
    N7(I)
    Hg(NO3)2
    inner-sphere coordination
    DMSO
    -
    -
    -4.8
    6
    N7(G)
    Na+
    eletrostatice interaction
    H2O
    234.0 (38eq.)
    234.2 (63eq.)
    +0.2
    7
    N7(G)
    Na+
    eletrostatice interaction
    H2O
    234.5 (38eq.)
    234.6 (63eq.)
    +0.1
    7
    N7(G)
    K+
    eletrostatice interaction
    H2O
    234.0 (0eq.)
    234.5 (24eq.)
    +0.5
    7
    N7(G)
    K+
    eletrostatice interaction
    H2O
    234.5 (0eq.)
    234.8 (24eq.)
    +0.3
    7
    N7(G)
    Co(NH3)63+
    outer-sphere binding
    H2O
    234.0 (0eq.)
    240.3 (5eq.)
    +6.3
    7
    N7(G)
    Co(NH3)63+
    outer-sphere binding
    H2O
    234.5 (0eq.)
    236.4 (5eq.)
    +1.9
    7
    N7(G)
    MgII
    not classified
    H2O
    234.0 (0eq.)
    233.7 (5eq.)
    -0.3
    7
    N7(G)
    MgII
    not classified
    H2O
    234.5 (0eq.)
    233.7 (5eq.)
    -0.8
    7
    N7(G)
    CdII
    not classified
    H2O
    234.0 (0eq.)
    227.7 (5eq.)
    -6.3
    7
    N7(G)
    CdII
    not classified
    H2O
    234.5 (0eq.)
    227.7 (5eq.)
    -6.8
    7
    N7(G)
    ZnII
    not classified
    H2O
    234.0 (0eq.)
    230.8 (5eq.)
    -3.2
    7
    N7(G)
    ZnII
    not classified
    H2O
    234.5 (0eq.)
    231.3 (5eq.)
    -3.2
    7
    Hydrogen-binding
    N1(A)
    H1-N1(G)
    hydrogen bond acceptor
    H2O
    206.8
    201.5
    -5.3
    8
    N7(G)
    H3-N3(C)
    hydrogen bond acceptor
    H2O
    236.2
    227.5
    -8.7
    9
    N7(A)
    H3-N3(T)
    hydrogen bond acceptor
    H2O
    232.3
    226.4
    -5.9
    9
    N7(A)
    NH2(G)
    hydrogen bond acceptor
    H2O
    231.6
    229.0
    -2.6
    10
    N1(G)
    N1(A)
    hydrogen bond donor
    H2O
    145.0
    147.5
    +2.5
    10
    NH2(A)
    O2(U)
    hydrogen bond donor
    H2O
    74.7
    80.0
    +5.3
    11
    NH2(G)
    O2(C)
    hydrogen bond donor
    H2O
    70.0
    71.7
    +1.7
    11
    N1(G)
    N3(C)
    hydrogen bond donor
    H2O
    145.0
    145.2
    +0.2
    11
    N1(G)
    N3(C)
    hydrogen bond donor
    H2O
    148.3
    145.9
    -2.4
    10
    N1(G)
    N3(C)
    hydrogen bond donor
    H2O
    145.4
    146.6
    +0.2
    12
    N1(G)
    O2(U)
    hydrogen bond donor
    H2O
    146.2
    139.8
    -6.4
    12
    N1(G)
    O2(U)
    hydrogen bond donor
    H2O
    145.4
    141.9
    -3.5
    12
    N1(G)
    O2(U)
    hydrogen bond donor
    H2O
    145.2
    141.7
    -3.5
    11
    NH2(G)
    N7(A)
    hydrogen bond donor
    H2O
    70.0
    74.1
    +4.1
    13
    NH2(A)
    N3(G)
    hydrogen bond donor
    H2O
    74.5
    79.2
    +4.7
    13
    NH2(A)
    O6(G)
    hydrogen bond donor
    H2O
    75.3
    83.5
    +8.2
    13
    NH2(C)
    O6(G)
    hydrogen bond donor
    H2O
    93.0
    98.3
    +5.3
    14
    NH2(C)
    O4(U)
    hydrogen bond donor
    H2O
    93.0
    95.6
    +2.6
    14
    1. 1. Tanaka, Y.; Kojima, C.; Morita, E. H.; Kasai, Y.; Yamasaki, K.; Ono, A.; Kainosho M.; Taira, K. J. Am. Chem. Soc. 2002, 124, 4595-4601.
    2. 2. Tanaka, Y.; Kasai, Y.; Mochizuki, S.; Wakisaka, A.; Morita, E. H.; Kojima, C.; Toyozawa, A.; Kondo, Y.; Taki, M.; Takagi, Y.; Inoue, A.; Yamasaki, K.; Taira, K. J. Am. Chem. Soc. 2004, 126, 744-752.
    3. 3. Tanaka, Y.; Taira, K. Chem. Commun. 2005, 2069-2079.
    4. 4. Wang, G.; Gaffney B. L.; Jones R. A. J. Am. Chem. Soc. 2004, 126, 8908-8909.
    5. 5. Buchanan, G. W.; Stothers, J. B. Can. J. Chem. 1982, 60, 787-791.
    6. 6. Buchanan, G. W.; Bell, M. J. Can. J. Chem. 1983, 61, 2445-2448.
    7. 7. Fan, Y.; Gaffney B. L.; Jones R. A. J. Am. Chem. Soc. 2005, 127, 17588-17589.
    8. 8. Gao, X.; Jones R. A. J. Am. Chem. Soc. 1987, 109, 3169-3171.
    9. 9. Gaffney, B. L.; Kung, P.-P.; Wang, C.; Jones R. A. J. Am. Chem. Soc. 1995, 117, 12281-12283.
    10. 10. Zhang, X.; Gaffney, B. L.; Jones R. A. J. Am. Chem. Soc. 1998, 120, 6625-6626.
    11. 11. Zhang, X.; Gaffney, B. L.; Jones R. A. J. Am. Chem. Soc. 1997, 119, 6432-6433.
    12. 12. Zhang, X.; Gaffney, B. L.; Jones R. A. J. Am. Chem. Soc. 1998, 120, 615-618.
    13. 13. Zhang, X.; Gaffney, B. L.; Jones R. A. J. Am. Chem. Soc. 1998, 120, 6625-6626.
    14. 14. Tanaka, Y.; Kojima, C.; Yamazaki, T.; Kodama, T. S.; Yasuno, K.; Miyashita, S.; Ono, A.; Ono, A.; Kainosho, M.; Kyogoku, Y. Biochemistry 2000, 39, 7074-7080.


  • 13C NMR data of N-metallated compounds

    13C-nuclus
    binding nuclus
    bond
    solvent
    free (ppm)
    bonded (ppm)
    Δ (ppm)
    ref.
    C8(G)
    CdCl2 (N7)
    inner-sphere coordination
    H2O
    -
    -
    +2.3
    1-3
    C8(G)
    MgCl2 (N7)
    not classified
    H2O
    -
    -
    +0.5
    1,3
    C8(G)
    ZnCl2 (N7)
    inner-sphere coordination
    H2O
    -
    -
    +2.5
    4
    C8(G)
    ZnCl2 (N7)
    inner-sphere coordination
    H2O
    -
    -
    +1.5
    4
    C8(G)
    Pt(en)Cl2 (N7)
    inner-sphere coordination
    H2O
    -
    -
    +1.1
    5
    C8(G)
    Pt(en)Cl2 (N7)
    inner-sphere coordination
    H2O
    -
    -
    +0.2
    5
    N7(G)
    NaClO4
    eletrostatice interaction
    H2O
    - (230 mM)
    - (800 mM)
    +0.1
    3
    1. 1. Tanaka, Y.; Kojima, C.; Morita, E. H.; Kasai, Y.; Yamasaki, K.; Ono, A.; Kainosho M.; Taira, K. J. Am. Chem. Soc. 2002, 124, 4595-4601.
    2. 2. Tanaka, Y.; Morita, E. H.; Hayashi, H.; Kasai, Y.; Tanaka T.; Taira, K. J. Am. Chem. Soc. 2000, 122, 11303-11310.
    3. 3. Tanaka, Y.; Taira, K. Chem. Commun. 2005, 2069-2079.
    4. 4. Jia, X.; Zon, G.; Marzilli, L. G. Inorg. Chem. 1991, 30, 228-239.
    5. 5. Mukundan, S., Jr.; Xu, Y.; Zon, G.; Marzilli, L. G. J. Am. Chem. Soc. 1991, 113, 3021-3027.


  • 13C NMR data of metal-acetylides and a metal-free acetylide

    Acetylides
    solvent
    δCi (ppm)
    Ph-C≡C-M
    δCt (ppm)
    Ph-C≡C-M
    ref.
    Ph-C≡C-Li
    THF
    n.r.
    139.35
    1
    Ph-C≡C-Al
    CDCl3
    107.5
    101.2
    2
    Ph-C≡C-Ga
    CDCl3
    107.2
    99.2
    2
    Ph-C≡C-Fe
    DMSO-d6
    119.0
    108.7
    3
    Ph-C≡C-Fe
    solvent
    132.4 - 132.7
    145.4 - 147.6
    4
    Ph-C≡C-Ru
    CD2Cl2
    110.9
    107.6
    5
    Ph-C≡C-Re
    solvent
    114.8 - 118.7
    105.9 - 117.1
    6
    (MeO)Ph-C≡C-Fe
    solvent
    119.5
    136.8
    4
    (Me)Ph-C≡C-Ru
    CD2Cl2
    109.5
    108.0
    5
    (HC≡C)Ph-C≡C-Re
    solvent
    113.9 - 118.8
    107.1 - 123.3
    6
    1. 1. T. F. Briggs, M. D. Winemiller, D. B. Collum, R. L. Parsons, Jr., A. H. Davulcu, G. D. Harris, J. M. Fortunak, P. N. Confalone, J. Am. Chem. Soc. 2004, 126, 5427-5435.
    2. 2. M. Schiefer, N. D. Reddy, H. J. Ahn, A. Stasch, H. W. Roesky, A. C. Schlicker, H. G. Schmidt, M. Noltemeyer, D. Vidovic Inorg. Chem. 2003, 42, 4970.
    3. 3. G. Albertin, P. Agnoletto, S. Antoniutti Polyhedron 2002, 21, 1755.
    4. 4. L. D. Field, A. J. Turnbull, P. Turner J. Am. Chem. Soc. 2002, 124, 3692.
    5. 5. G. Albertin, S. Antoniutti, E. Bordignon, M. Granzotto J. Organomet. Chem. 1999, 585, 83.
    6. 6. G. Albertin, S. Antoniutti, E. Bordignon, D. Bresolin J. Organomet. Chem. 2000, 609, 10.

Design: HTML5 UP