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_4125766
_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         'C18 H13 N3 O Pd'
_chemical_formula_sum            'C18 H13 N3 O Pd'
_chemical_formula_weight         393.71
_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
_audit_creation_date             2016-11-23
_audit_creation_method
;
Olex2 1.2
(compiled 2016.08.25 svn.r3337 for OlexSys, GUI svn.r5221)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.167(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.6497(8)
_cell_length_b                   13.959(2)
_cell_length_c                   16.001(2)
_cell_measurement_reflns_used    2108
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      69.7800
_cell_measurement_theta_min      4.2230
_cell_volume                     1473.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w   -173.00 -11.00   1.00   16.00    -- -101.00   0.00 -36.00  162
  2  \w   -120.00  58.00   1.00   16.00    --  -32.00   0.00 -36.00  178
  3  \w    -91.00 -21.00   1.00   16.00    -- -101.00  72.00-180.00   70
  4  \w   -135.00 -11.00   1.00   16.00    -- -101.00  72.00 108.00  124
  5  \w   -137.00-106.00   1.00   16.00    -- -101.00 -72.00 -36.00   31
  6  \w   -106.00 -19.00   1.00   16.00    -- -101.00  72.00 -36.00   87
  7  \w   -149.00 -72.00   1.00   16.00    -- -101.00 -72.00  36.00   77
  8  \w   -191.00-161.00   1.00   16.00    -- -101.00 -72.00 108.00   30
  9  \w    -53.00 -23.00   1.00   16.00    -- -101.00  72.00  36.00   30
 10  \w   -173.00 -11.00   1.00   16.00    -- -101.00   0.00  36.00  162
 11  \w   -117.00  52.00   1.00   16.00    --  -32.00   0.00-108.00  169
 12  \w   -133.00 -28.00   1.00   16.00    -- -101.00  72.00-108.00  105
 13  \w   -191.00-136.00   1.00   16.00    -- -101.00 -72.00-108.00   55
 14  \w   -174.00 -87.00   1.00   16.00    -- -101.00 -72.00-180.00   87
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1691349000
_diffrn_orient_matrix_UB_12      0.0737278000
_diffrn_orient_matrix_UB_13      0.0250974000
_diffrn_orient_matrix_UB_21      -0.0713310000
_diffrn_orient_matrix_UB_22      0.0099000000
_diffrn_orient_matrix_UB_23      0.0875386000
_diffrn_orient_matrix_UB_31      0.1441168000
_diffrn_orient_matrix_UB_32      -0.0816389000
_diffrn_orient_matrix_UB_33      0.0334316000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.2188
_diffrn_reflns_av_unetI/netI     0.1327
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            12646
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.500
_diffrn_reflns_theta_max         64.982
_diffrn_reflns_theta_min         4.217
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.219
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48923
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.775
_exptl_crystal_F_000             784
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.12
_refine_diff_density_max         2.294
_refine_diff_density_min         -3.208
_refine_diff_density_rms         0.468
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.181
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         2507
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.173
_refine_ls_R_factor_all          0.1825
_refine_ls_R_factor_gt           0.1212
_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^)+(0.2000P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2936
_refine_ls_wR_factor_ref         0.3805
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1406
_reflns_number_total             2507
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b10309_si_005.cif
_cod_data_source_block           dm-ad-161116_cu
_cod_database_code               4125766
_shelxl_version_number           2012-9
_reflns_odcompleteness_completeness 95.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.40
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(N1) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(C9) \\sim
Ueq, Uanis(C15) \\sim Ueq, Uanis(C16) \\sim Ueq: with sigma of 0.001 and sigma
for terminal atoms of 0.001
3.a Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C9(H9), C13(H13), C15(H15), C14(H14), C2(H2), C4(H4),
 C5(H5), C3(H3)
3.b Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C)
;
_shelx_res_checksum              20313
_shelx_hkl_checksum              69101
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.964
_oxdiff_exptl_absorpt_empirical_full_min 0.524