Experimental and Theoretical Studies on Ru(II)-Catalyzed Oxidative C‒H/C‒H Coupling of Phenols with Aromatic Amides Using Air as Oxidant: Scope, Synthetic Applications, and Mechanistic Insights
Zhang, Luoqiang; Zhu, Lei; Zhang, Yuming; Yang, Yudong; Wu, Yimin; Ma, Weixin; Lan, Yu; You, Jingsong; ACS Catalysis 8 (2018) 8324–; doi:10.1021/acscatal.8b02816

data_4515727
_publ_section_title
;
 Experimental and Theoretical Studies on Ru(II)-Catalyzed Oxidative
 C--H/C--H Coupling of Phenols with Aromatic Amides Using Air as Oxidant:
 Scope, Synthetic Applications, and Mechanistic Insights
;
_journal_issue                   9
_journal_name_full               'ACS Catalysis'
_journal_page_first              8324
_journal_paper_doi               10.1021/acscatal.8b02816
_journal_volume                  8
_journal_year                    2018
_chemical_formula_moiety         'C33 H39 N2 O2 Ru, F6 Sb'
_chemical_formula_sum            'C33 H39 F6 N2 O2 Ru Sb'
_chemical_formula_weight         832.48
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-05-23
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.3993(17)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.2275(2)
_cell_length_b                   10.9193(2)
_cell_length_c                   24.4944(4)
_cell_measurement_reflns_used    5367
_cell_measurement_temperature    293.4(5)
_cell_measurement_theta_max      72.6000
_cell_measurement_theta_min      4.0460
_cell_volume                     3499.90(10)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      293.4(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_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   -104.00 -20.00   1.00    1.22    --  -36.29 -57.00  30.00   84
  2  \w    -53.00  31.00   1.00    1.22    --  -36.29  57.00-180.00   84
  3  \w   -108.00  -7.00   1.00    1.22    --  -36.29 -19.00-180.00  101
  4  \w      1.00  75.00   1.00    1.22    --   36.29 -99.00-180.00   74
  5  \w     23.00  90.00   1.00    1.22    --   36.29-125.00  90.00   67
  6  \w    -31.00  53.00   1.00    1.22    --   36.29 -57.00-120.00   84
  7  \w     91.00 176.00   1.00    4.89    --  108.71  61.00-180.00   85
  8  \w     39.00 109.00   1.00    4.89    --  108.71 -94.00 120.00   70
  9  \w     40.00 126.00   1.00    4.89    --  108.71 -45.00 150.00   86
 10  \w     42.00 127.00   1.00    4.89    --  108.71 -61.00  60.00   85
 11  \w     39.00  69.00   1.00    4.89    --  108.71-111.00  60.00   30
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1139951000
_diffrn_orient_matrix_UB_12      0.0254946000
_diffrn_orient_matrix_UB_13      -0.0020765000
_diffrn_orient_matrix_UB_21      0.0182956000
_diffrn_orient_matrix_UB_22      -0.1377916000
_diffrn_orient_matrix_UB_23      -0.0078699000
_diffrn_orient_matrix_UB_31      -0.0233456000
_diffrn_orient_matrix_UB_32      0.0164364000
_diffrn_orient_matrix_UB_33      -0.0630730000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0484
_diffrn_reflns_av_unetI/netI     0.0479
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            18727
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.840
_diffrn_reflns_theta_min         3.648
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.164
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42556
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.580
_exptl_crystal_description       block
_exptl_crystal_F_000             1664
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.4
_refine_diff_density_max         1.576
_refine_diff_density_min         -1.638
_refine_diff_density_rms         0.150
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     413
_refine_ls_number_reflns         6892
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.0668
_refine_ls_R_factor_gt           0.0596
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1031P)^2^+6.0651P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1555
_refine_ls_wR_factor_ref         0.1654
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5977
_reflns_number_total             6892
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b02816_si_004.cif
_cod_data_source_block           yjs-333
_cod_original_cell_volume        3499.90(12)
_cod_database_code               4515727
_reflns_odcompleteness_completeness 86.73
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C00V(H00V)
2.b Aromatic/amide H refined with riding coordinates:
 N004(H004), C00D(H00D), C00E(H00E), C00G(H00G), C00I(H00I), C00K(H00K),
 C00L(H00L), C00M(H00M), C00N(H00N), C00P(H00P), C00R(H00R), C00S(H00S),
 C00T(H00T), C00X(H00X), C011(H011), C013(H013), C014(H014)
2.c Idealised Me refined as rotating group:
 C00Y(H00A,H00B,H00C), C010(H01A,H01B,H01C), C012(H01D,H01E,H01F), C016(H01G,
 H01H,H01I), C017(H01J,H01K,H01L), C018(H01M,H01N,H01O), C019(H01P,H01Q,H01R)
;
_shelx_res_checksum              21200
_shelx_hkl_checksum              96153
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2017-05-23
_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 1.899
_oxdiff_exptl_absorpt_empirical_full_min 0.692