Precatalyst Effects on Pd-Catalyzed Cross-Coupling Difluoromethylation of Aryl Boronic Acids
Hori, Kaishi; Motohashi, Hirotaka; Saito, Daichi; Mikami, Koichi; ACS Catalysis 9 (2018) 417–; doi:10.1021/acscatal.8b03892

data_4515485
_publ_section_title
;
 Precatalyst Effects on Pd-Catalyzed Cross-Coupling Difluoromethylation of
 Aryl Boronic Acids
;
_journal_issue                   1
_journal_name_full               'ACS Catalysis'
_journal_page_first              417
_journal_paper_doi               10.1021/acscatal.8b03892
_journal_volume                  9
_journal_year                    2018
_chemical_formula_moiety         'C37 H31 F2 I P2 Pd'
_chemical_formula_sum            'C37 H31 F2 I P2 Pd'
_chemical_formula_weight         808.86
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-12-26
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.350(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.0900(10)
_cell_length_b                   15.2246(14)
_cell_length_c                   20.0614(18)
_cell_measurement_reflns_used    7270
_cell_measurement_temperature    100
_cell_measurement_theta_max      75.9270
_cell_measurement_theta_min      4.3640
_cell_volume                     3691.6(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.40b (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.40b (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.40b (Rigaku OD, 2017)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.978
_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    -78.00  46.00   0.25    0.25    --  -43.10  54.00-135.51  496
  2  \w    -26.00   5.00   0.25    0.25    --  -43.10  57.00  90.00  124
  3  \w    -53.00  43.00   0.25    0.25    --  -43.10  57.00 -30.00  384
  4  \w   -196.00 -82.00   0.25    1.00    -- -110.00 -38.00  60.00  456
  5  \w   -152.00 -78.00   0.25    1.00    -- -110.00  38.00  60.00  296
  6  \w    -60.00 -21.00   0.25    1.00    -- -110.00  38.00  60.00  156
  7  \w   -127.00 -76.00   0.25    1.00    -- -110.00 -57.00-150.00  204
  8  \w   -169.00-141.00   0.25    1.00    -- -110.00 -57.00-150.00  112
  9  \w   -140.00-114.00   0.25    1.00    -- -110.00 -57.00  90.00  104
 10  \w   -142.00-100.00   0.25    1.00    -- -110.00 -38.00 -60.00  168
 11  \w   -137.00 -62.00   0.25    1.00    -- -110.00  72.00-180.00  300
 12  \w   -121.00 -28.00   0.25    1.00    -- -110.00  72.00-120.00  372
 13  \w   -144.00 -39.00   0.25    1.00    -- -110.00  57.00  30.00  420
 14  \w   -145.00 -28.00   0.25    1.00    -- -110.00  57.00-180.00  468
 15  \w    -99.00 -73.00   0.25    1.00    -- -110.00  72.00 120.00  104
 16  \w    -58.00 -33.00   0.25    1.00    -- -110.00  57.00 120.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RCD3): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0391156000
_diffrn_orient_matrix_UB_12      -0.0960746000
_diffrn_orient_matrix_UB_13      -0.0000233000
_diffrn_orient_matrix_UB_21      -0.1139744000
_diffrn_orient_matrix_UB_22      0.0299764000
_diffrn_orient_matrix_UB_23      -0.0281761000
_diffrn_orient_matrix_UB_31      0.0416245000
_diffrn_orient_matrix_UB_32      -0.0109642000
_diffrn_orient_matrix_UB_33      -0.0714094000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0669
_diffrn_reflns_av_unetI/netI     0.0444
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            11170
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.229
_diffrn_reflns_theta_min         4.409
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    11.703
_exptl_absorpt_correction_T_max  0.730
_exptl_absorpt_correction_T_min  0.581
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.40b (Rigaku Oxford Diffraction, 2017)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.455
_exptl_crystal_description       block
_exptl_crystal_F_000             1600
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.053
_exptl_crystal_size_min          0.045
_refine_diff_density_max         1.014
_refine_diff_density_min         -1.280
_refine_diff_density_rms         0.166
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     213
_refine_ls_number_reflns         3316
_refine_ls_number_restraints     47
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.1084
_refine_ls_R_factor_gt           0.0958
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0139P)^2^+151.7359P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1803
_refine_ls_wR_factor_ref         0.1902
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2908
_reflns_number_total             3316
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b03892_si_002.cif
_cod_data_source_block           exp_554
_cod_database_code               4515485
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C37 H31 F2 I P2 Pd'
_reflns_odcompleteness_completeness 97.25
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Uiso/Uaniso restraints and constraints
Pd00 \\sim F2 \\sim C3 \\sim I02 \\sim F1: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002
3. Rigid body (RIGU) restrains
 Pd00, C3, I02, F2, F1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Fixed Sof: I02(0.5) F1(0.5) F2(0.5) C3(0.5) H3(0.5)
5.a Ternary CH refined with riding coordinates:
 C3(H3)
5.b Aromatic/amide H refined with riding coordinates:
 C004(H004), C006(H006), C008(H008), C009(H009), C00B(H00B), C00C(H00C),
 C00D(H00D), C00E(H00E), C00F(H00F), C00G(H00G), C00I(H00I), C00J(H00J),
 C00K(H00K), C00L(H00L), C00M(H00M)
;
_shelx_res_checksum              55471
_shelx_hkl_checksum              65941
_shelx_fab_checksum              81689
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.688
_oxdiff_exptl_absorpt_empirical_full_min 0.593