Detailed Mechanistic Studies on Palladium-Catalyzed Selective C-H Olefination with Aliphatic Alkenes: A Significant Influence of Proton Shuttling.
Deb, Arghya; Hazra, Avijit; Peng, Qian; Paton, Robert S.; Maiti, Debabrata; Journal of the American Chemical Society 139 (2017) 763–775; doi:10.1021/jacs.6b10309

data_4125765
_publ_section_title
;
 Detailed Mechanistic Studies on Palladium-Catalyzed Selective C-H
 Olefination with Aliphatic Alkenes: A Significant Influence of Proton
 Shuttling.
;
_journal_issue                   2
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              763
_journal_page_last               775
_journal_paper_doi               10.1021/jacs.6b10309
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety         'C19 H15 N3 O Pd'
_chemical_formula_sum            'C19 H15 N3 O Pd'
_chemical_formula_weight         378.68
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-11-13
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Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
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_cell_angle_alpha                90
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_cell_length_c                   26.898(6)
_cell_measurement_temperature    100(2)
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_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
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_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details
;
scan:
    Number of images: 280
               Slice: -96.0000 - 44.0000
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       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 0.0000
                 Phi: 108.0000
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scan:
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scan:
    Number of images: 60
               Slice: -31.0000 - -1.0000
         Image width: 0.5000
            Exp time: 8.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 72.0000
                 Phi: -108.0000
                 XTD: 44.9560
              2theta: -19.9421
scan:
    Number of images: 360
               Slice: -110.0000 - 70.0000
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       Rotation axis: Omega
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scan:
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               Slice: -51.5000 - -16.5000
         Image width: 0.5000
            Exp time: 8.0000
       Rotation axis: Omega
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              2theta: -19.9421
scan:
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               Slice: -65.5000 - -35.0000
         Image width: 0.5000
            Exp time: 8.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: -72.0000
                 Phi: -108.0000
                 XTD: 44.9560
              2theta: -19.9421
;
_diffrn_measurement_device
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AFC12 (Right): Kappa 3 circle
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_diffrn_measurement_specimen_support Fiber
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_diffrn_orient_matrix_UB_31      0.001032
_diffrn_orient_matrix_UB_32      0.033770
_diffrn_orient_matrix_UB_33      -0.016022
_diffrn_radiation_monochromator  Confocal
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_diffrn_reflns_av_unetI/netI     0.0360
_diffrn_reflns_Laue_measured_fraction_full 0.996
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_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            18865
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.150
_diffrn_reflns_theta_min         3.103
_diffrn_source_current           0.6
_diffrn_source_power             0.0
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.191
_exptl_crystal_density_diffrn    1.609
_exptl_crystal_F_000             748
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.188
_refine_diff_density_min         -0.938
_refine_diff_density_rms         0.108
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.873
_refine_ls_hydrogen_treatment    constr
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_refine_ls_number_reflns         4181
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_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
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;
 w=1/[\s^2^(Fo^2^)+(0.1000P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
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_cod_database_code               4125765
_shelxl_version_number           2012-9
_shelx_estimated_absorpt_t_max   0.797
_shelx_estimated_absorpt_t_min   0.797
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), C8(H8), C12(H12), C13(H13), C15(H15), C17(H17),
 C18(H18), C19(H19)
2.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C)
;
_shelx_res_checksum              93459
_shelx_hkl_checksum              51140
_olex2_submission_special_instructions 'No special instructions were received'