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_4125764
_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 H14 F N3 O Pd'
_chemical_formula_sum            'C19 H14 F N3 O Pd'
_chemical_formula_weight         425.73
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-01-01
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.536(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.817(3)
_cell_length_b                   8.561(4)
_cell_length_c                   27.641(12)
_cell_measurement_reflns_used    4381
_cell_measurement_temperature    150
_cell_measurement_theta_max      29.2
_cell_measurement_theta_min      3.1
_cell_volume                     1613.1(12)
_computing_cell_refinement
;
CrystalClear-SM Expert 2.1 b28 (Rigaku, 2013)
;
_computing_data_collection
;
CrystalClear-SM Expert 2.1 b28 (Rigaku, 2013)
;
_computing_data_reduction
;
CrystalClear-SM Expert 2.1 b28 (Rigaku, 2013)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_temperature      150
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_details
;
scan:
    Number of images: 351
               Slice: -105.5000 - 70.0000
         Image width: 0.5000
            Exp time: 8.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 0.0000
                 Phi: -108.0000
                 XTD: 44.9316
              2theta: -19.9496
scan:
    Number of images: 60
               Slice: -35.0000 - -5.0000
         Image width: 0.5000
            Exp time: 8.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: -72.0000
                 Phi: -180.0000
                 XTD: 44.9316
              2theta: -19.9496
scan:
    Number of images: 308
               Slice: -110.0000 - 44.0000
         Image width: 0.5000
            Exp time: 8.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 0.0000
                 Phi: -180.0000
                 XTD: 44.9316
              2theta: -19.9496
scan:
    Number of images: 95
               Slice: -11.0000 - 36.5000
         Image width: 0.5000
            Exp time: 8.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 72.0000
                 Phi: -180.0000
                 XTD: 44.9316
              2theta: -19.9496
scan:
    Number of images: 219
               Slice: -110.0000 - -0.5000
         Image width: 0.5000
            Exp time: 8.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 0.0000
                 Phi: -36.0000
                 XTD: 44.9316
              2theta: -19.9496
;
_diffrn_measurement_device
;
AFC12 (Right): Kappa 3 circle
;
_diffrn_measurement_device_type
;
Rigaku Saturn724+ (4x4 bin mode)
;
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support Fiber
_diffrn_orient_matrix_type       XPlain
_diffrn_orient_matrix_UB_11      0.086452
_diffrn_orient_matrix_UB_12      -0.060873
_diffrn_orient_matrix_UB_13      -0.101706
_diffrn_orient_matrix_UB_21      0.065209
_diffrn_orient_matrix_UB_22      0.096873
_diffrn_orient_matrix_UB_23      -0.002551
_diffrn_orient_matrix_UB_31      0.021328
_diffrn_orient_matrix_UB_32      -0.013677
_diffrn_orient_matrix_UB_33      0.025827
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0600
_diffrn_reflns_av_unetI/netI     0.0636
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            15082
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         3.071
_diffrn_source                   MicroMax003_Mo
_diffrn_source_current           0.6
_diffrn_source_power             0.0
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.173
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.621
_exptl_absorpt_correction_type   numerical
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.753
_exptl_crystal_description       Prism
_exptl_crystal_F_000             848
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.592
_refine_diff_density_min         -0.807
_refine_diff_density_rms         0.139
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.161
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     227
_refine_ls_number_reflns         2798
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.161
_refine_ls_R_factor_all          0.0651
_refine_ls_R_factor_gt           0.0445
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0518P)^2^+0.7204P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1020
_refine_ls_wR_factor_ref         0.1202
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2220
_reflns_number_total             2798
_reflns_shell_number_unique_all  4417
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b10309_si_002.cif
_cod_data_source_block           shelxl
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_absorpt_correction_type' value 'Numerical' changed to
'numerical' according to
/home/data/users/saulius/crontab/automatic-downloads/current/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 
;
_cod_database_code               4125764
_shelx_estimated_absorpt_t_max   0.799
_shelx_estimated_absorpt_t_min   0.799
_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:
 C12(H12A,H12B)
2.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C14(H14), C17(H17), C18(H18), C20(H20), C22(H22), C23(H23),
 C24(H24), C25(H25)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'