Ruthenium-Catalyzed Direct C‒H Amidation of Arenes: A Mechanistic Study
Zhang, Lu−Lu; Li, Lian-Hua; Wang, Yu-Qi; Yang, Yan-Fang; Liu, Xue-Yuan; Liang, Yong-Min; Organometallics 33 (2014) 1905–; doi:10.1021/om500080z

data_4083052
_publ_section_title
;
 Ruthenium-Catalyzed Direct C--H Amidation of Arenes: A Mechanistic Study
;
_journal_issue                   8
_journal_name_full               Organometallics
_journal_page_first              1905
_journal_paper_doi               10.1021/om500080z
_journal_volume                  33
_journal_year                    2014
_chemical_formula_moiety         'C21 H22 Cl N Ru'
_chemical_formula_sum            'C21 H22 Cl N Ru'
_chemical_formula_weight         424.91
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yab'
_space_group_name_H-M_alt        'P 1 21/a 1'
_symmetry_space_group_name_Hall  '-P 2yab'
_symmetry_space_group_name_H-M   'P 1 21/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2013-12-27
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.939(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.0631(8)
_cell_length_b                   7.8858(2)
_cell_length_c                   16.5738(11)
_cell_measurement_reflns_used    4157
_cell_measurement_temperature    293.12(16)
_cell_measurement_theta_max      28.6065
_cell_measurement_theta_min      2.9566
_cell_volume                     1838.70(19)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      293.12(16)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.899
_diffrn_measurement_details
;
  1 omega   52.00  102.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  178.0000  -30.0000 50

  2 omega   -8.00   94.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867   77.0000 -180.0000 102

  3 omega   52.00   79.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  178.0000   90.0000 27

  4 omega   42.00   68.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  -99.0000   30.0000 26

  5 omega   35.00   64.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  -99.0000   60.0000 29

  6 omega  -50.00   22.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  -77.0000  -30.0000 72
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0220204000
_diffrn_orient_matrix_UB_12      0.0215101000
_diffrn_orient_matrix_UB_13      -0.0443071000
_diffrn_orient_matrix_UB_21      0.0309968000
_diffrn_orient_matrix_UB_22      -0.0562972000
_diffrn_orient_matrix_UB_23      -0.0105580000
_diffrn_orient_matrix_UB_31      -0.0331676000
_diffrn_orient_matrix_UB_32      -0.0668693000
_diffrn_orient_matrix_UB_33      -0.0053716000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0302
_diffrn_reflns_av_unetI/netI     0.0412
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.899
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            9871
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.899
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.657
_diffrn_reflns_theta_min         2.961
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.999
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67543
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.535
_exptl_crystal_description       block
_exptl_crystal_F_000             864
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.38
_exptl_crystal_size_min          0.36
_refine_diff_density_max         0.469
_refine_diff_density_min         -0.560
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     220
_refine_ls_number_reflns         4254
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0399
_refine_ls_R_factor_gt           0.0303
_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^)+(0.0210P)^2^+0.6952P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0619
_refine_ls_wR_factor_ref         0.0680
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3541
_reflns_number_total             4254
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om500080z_si_002.cif
_cod_data_source_block           zhangll0111
_cod_depositor_comments
'Adding full bibliography for 4083051--4083052.cif.'
_cod_database_code               4083052
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 99.70
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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:
 C19(H19)
2.b Aromatic/amide H refined with riding coordinates:
 C17(H17), C14(H14), C5(H5), C11(H11), C16(H16), C4(H4), C2(H2), C9(H9),
 C10(H10), C8(H8), C3(H3), C13(H13)
2.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C18(H18A,H18B,H18C), C21(H21A,H21B,H21C)
;
_shelx_res_checksum              95782
_shelx_hkl_checksum              92848