Ligand-Promoted Direct C‒H Arylation of Simple Arenes: Evidence for a Cooperative Bimetallic Mechanism
Kim, Jaewoon; Hong, Soon Hyeok; ACS Catalysis 7 (2017) 3336–; doi:10.1021/acscatal.7b00397

data_4514080
_publ_section_title
;
 Ligand-Promoted Direct C--H Arylation of Simple Arenes: Evidence for a
 Cooperative Bimetallic Mechanism
;
_journal_issue                   5
_journal_name_full               'ACS Catalysis'
_journal_page_first              3336
_journal_paper_doi               10.1021/acscatal.7b00397
_journal_volume                  7
_journal_year                    2017
_chemical_formula_moiety         'C38 H52 N2 O2 Pd'
_chemical_formula_sum            'C38 H52 N2 O2 Pd'
_chemical_formula_weight         675.21
_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             2016-11-10
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.4700(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.47076(8)
_cell_length_b                   21.63215(13)
_cell_length_c                   13.10657(8)
_cell_measurement_reflns_used    44575
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      76.3970
_cell_measurement_theta_min      4.1260
_cell_volume                     3487.57(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43d (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)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2262
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_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    -69.00  32.00   1.00    1.00    --  -41.24  57.00 -30.00  101
  2  \w   -117.00  -9.00   1.00    1.00    --  -41.24 -77.00-150.00  108
  3  \w      1.00  82.00   1.00    1.00    --   41.24 -99.00-120.00   81
  4  \w     23.00  97.00   1.00    1.00    --   41.24-125.00  56.00   74
  5  \w     17.00 116.00   1.00    1.00    --   41.24  38.00-180.00   99
  6  \w    -33.00  66.00   1.00    1.00    --   41.24 -38.00  30.00   99
  7  \w     39.00 138.00   1.00    1.79    --  112.00 -45.00  30.00   99
  8  \w     36.00 116.00   1.00    1.79    --  112.00-111.00 -30.00   80
  9  \w     29.00 109.00   1.00    1.79    --  112.00 -94.00  60.00   80
 10  \w     36.00 145.00   1.00    1.79    --  112.00 -77.00 -30.00  109
 11  \w     86.00 178.00   1.00    1.79    --  112.00  45.00 -30.00   92
 12  \w     29.00 109.00   1.00    1.79    --  112.00 -94.00 -30.00   80
 13  \w     84.00 178.00   1.00    1.79    --  112.00  30.00  60.00   94
 14  \w     36.00 116.00   1.00    1.79    --  112.00-111.00  60.00   80
 15  \w     36.00 140.00   1.00    1.79    --  112.00 -30.00 120.00  104
 16  \w     39.00 138.00   1.00    1.79    --  112.00 -45.00-120.00   99
 17  \w     36.00 116.00   1.00    1.79    --  112.00-111.00 -60.00   80
 18  \w     36.00 116.00   1.00    1.79    --  112.00-111.00-150.00   80
 19  \w     29.00 109.00   1.00    1.79    --  112.00 -94.00 120.00   80
 20  \w     30.00 165.00   1.00    1.79    --  112.00 -15.00  60.00  135
 21  \w     29.00 109.00   1.00    1.79    --  112.00 -94.00 150.00   80
 22  \w     36.00 116.00   1.00    1.79    --  112.00-111.00 -90.00   80
 23  \w     29.00 109.00   1.00    1.79    --  112.00 -94.00-180.00   80
 24  \w     39.00 138.00   1.00    1.79    --  112.00 -45.00 120.00   99
 25  \w     36.00 116.00   1.00    1.79    --  112.00-111.00 120.00   80
 26  \w     36.00 145.00   1.00    1.79    --  112.00 -77.00-150.00  109
 27  \w     86.00 178.00   1.00    1.79    --  112.00  45.00  60.00   92
 28  \w     24.00 178.00   1.00    1.79    --  112.00   0.00 -60.00  154
 29  \w   -113.00 -13.00   1.00    1.00    --  -41.24 -57.00   0.00  100
 30  \w    -96.00  -2.00   1.00    1.00    --  -41.24 125.00 133.00   94
 31  \w   -117.00  -9.00   1.00    1.00    --  -41.24 -77.00 -30.00  108
 32  \w   -113.00 -13.00   1.00    1.00    --  -41.24 -57.00-120.00  100
 33  \w   -117.00  -9.00   1.00    1.00    --  -41.24 -77.00  90.00  108
 34  \w   -113.00 -13.00   1.00    1.00    --  -41.24 -57.00  90.00  100
 35  \w      9.00 117.00   1.00    1.00    --   41.24  77.00-180.00  108
 36  \w     84.00 178.00   1.00    1.79    --  112.00  30.00 150.00   94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1072257000
_diffrn_orient_matrix_UB_12      -0.0062493000
_diffrn_orient_matrix_UB_13      -0.0431440000
_diffrn_orient_matrix_UB_21      0.0140684000
_diffrn_orient_matrix_UB_22      0.0707862000
_diffrn_orient_matrix_UB_23      0.0043302000
_diffrn_orient_matrix_UB_31      0.0632122000
_diffrn_orient_matrix_UB_32      -0.0050755000
_diffrn_orient_matrix_UB_33      0.1109133000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0397
_diffrn_reflns_av_unetI/netI     0.0165
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            70688
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.610
_diffrn_reflns_theta_min         3.593
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.542
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68147
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43d (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light bronze'
_exptl_crystal_density_diffrn    1.286
_exptl_crystal_description       block
_exptl_crystal_F_000             1424
_exptl_crystal_size_max          0.262
_exptl_crystal_size_mid          0.079
_exptl_crystal_size_min          0.073
_refine_diff_density_max         0.713
_refine_diff_density_min         -0.713
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     400
_refine_ls_number_reflns         7324
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0259
_refine_ls_R_factor_gt           0.0247
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0260P)^2^+3.5390P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0608
_refine_ls_wR_factor_ref         0.0616
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7034
_reflns_number_total             7324
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs7b00397_si_002.cif
_cod_data_source_block           exp_426
_cod_depositor_comments          'Adding full bibliography for 4514080.cif.'
_cod_original_cell_volume        3487.56(4)
_cod_database_code               4514080
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         C38H52N2O2Pd1
_chemical_oxdiff_usercomment     kjw11-57/DCM
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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.a Ternary CH refined with riding coordinates:
 C12(H12), C21(H21), C9(H9), C24(H24)
2.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C29(H29), C17(H17), C31(H31), C2(H2), C1(H1), C32(H32), C19(H19),
 C6(H6), C28(H28), C5(H5), C18(H18)
2.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C33(H33A,H33B,H33C), C26(H26A,H26B,
 H26C), C14(H14A,H14B,H14C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C10(H10A,
 H10B,H10C), C25(H25A,H25B,H25C), C38(H38A,H38B,H38C), C37(H37A,H37B,H37C),
 C36(H36A,H36B,H36C)
;
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.333
_oxdiff_exptl_absorpt_empirical_full_min 0.795