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_4515725
_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         'C22 H24 Cl N O Ru'
_chemical_formula_sum            'C22 H24 Cl N O Ru'
_chemical_formula_weight         454.94
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-05-16
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.939(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.6782(5)
_cell_length_b                   8.2226(4)
_cell_length_c                   20.4400(10)
_cell_measurement_reflns_used    5322
_cell_measurement_temperature    298.0(2)
_cell_measurement_theta_max      72.6550
_cell_measurement_theta_min      5.3210
_cell_volume                     1933.30(16)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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      298.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_details
;
  1 omega   20.00  104.00   1.0000    2.6600
omega____ theta____ kappa____ phi______ frames
    -       36.4171   57.0000 -150.0000 84

  2 omega  -31.00   53.00   1.0000    2.6600
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -57.0000  -90.0000 84

  3 omega    1.00   75.00   1.0000    2.6600
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -99.0000 -180.0000 74

  4 omega   23.00   90.00   1.0000    2.6600
omega____ theta____ kappa____ phi______ frames
    -       36.4171 -125.0000    0.0000 67

  5 omega    1.00   75.00   1.0000    2.6600
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -99.0000 -120.0000 74

  6 omega  -33.00   55.00   1.0000    2.6600
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -38.0000  -60.0000 88

  7 omega   90.00  175.00   1.0000   10.6500
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -90.0000 85

  8 omega   40.00   98.00   1.0000   10.6500
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  120.0000 58

  9 omega   40.00   98.00   1.0000   10.6500
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000   60.0000 58

 10 omega   40.00   98.00   1.0000   10.6500
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -180.0000 58

 11 omega   38.00   91.00   1.0000   10.6500
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000    0.0000 53

 12 omega   38.00   91.00   1.0000   10.6500
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000   60.0000 53

 13 omega   40.00   98.00   1.0000   10.6500
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -60.0000 58

 14 omega   40.00   98.00   1.0000   10.6500
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000    0.0000 58

 15 omega   38.00  116.00   1.0000   10.6500
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000   90.0000 78

 16 omega   41.00  126.00   1.0000   10.6500
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000  150.0000 85

 17 omega   20.00  104.00   1.0000    2.6600
omega____ theta____ kappa____ phi______ frames
    -       36.4171   57.0000   90.0000 84

 18 omega  -31.00   28.00   1.0000    2.6600
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -57.0000   60.0000 59

 19 omega   10.00  104.00   1.0000    2.6600
omega____ theta____ kappa____ phi______ frames
    -       36.4171   77.0000  -30.0000 94
;
_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_UB_11      -0.0903352000
_diffrn_orient_matrix_UB_12      0.0597469000
_diffrn_orient_matrix_UB_13      0.0412650000
_diffrn_orient_matrix_UB_21      0.0982836000
_diffrn_orient_matrix_UB_22      0.0348313000
_diffrn_orient_matrix_UB_23      0.0589261000
_diffrn_orient_matrix_UB_31      0.0112963000
_diffrn_orient_matrix_UB_32      0.1741123000
_diffrn_orient_matrix_UB_33      -0.0260254000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0430
_diffrn_reflns_av_unetI/netI     0.0357
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            11402
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.615
_diffrn_reflns_theta_min         4.745
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.906
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.34851
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dull orangish orange'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.563
_exptl_crystal_description       plate
_exptl_crystal_F_000             928
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.919
_refine_diff_density_min         -0.843
_refine_diff_density_rms         0.123
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     239
_refine_ls_number_reflns         3772
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0505
_refine_ls_R_factor_gt           0.0469
_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^)+(0.0950P)^2^+0.1778P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1227
_refine_ls_wR_factor_ref         0.1292
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3409
_reflns_number_total             3772
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b02816_si_003.cif
_cod_data_source_block           yjs-0002
_cod_database_code               4515725
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C00I(H00I)
2.b Aromatic/amide H refined with riding coordinates:
 C006(H006), C009(H009), C00A(H00A), C00B(H00B), C00C(H00C), C00D(H00D),
 C00E(H00E), C00J(H00J), C00K(H00K), C00L(H00L), C00N(H00N)
2.c Idealised Me refined as rotating group:
 C00M(H00F,H00G,H00H), C00O(H00M,H00O,H00P), C00P(H00Q,H00R,H00S), C00Q(H00T,
 H00U,H00V)
;
_shelx_res_checksum              84604
_shelx_hkl_checksum              34728
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2017-05-15
_olex2_submission_special_instructions 'No special instructions were received'