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_4083051
_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         'C27 H26 Cl N3 O4 Ru S'
_chemical_formula_sum            'C27 H26 Cl N3 O4 Ru S'
_chemical_formula_weight         625.09
_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     iterative
_audit_creation_date             2013-06-28
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.8750(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.18468(10)
_cell_length_b                   11.04538(14)
_cell_length_c                   29.0948(4)
_cell_measurement_reflns_used    8374
_cell_measurement_temperature    292.1(8)
_cell_measurement_theta_max      70.7210
_cell_measurement_theta_min      5.0230
_cell_volume                     2616.44(6)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      292.1(8)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9312
_diffrn_measured_fraction_theta_max 0.9966
_diffrn_measurement_details
;
  1 omega  -16.00   29.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000  -60.0000 45

  2 omega  -76.00  -50.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000   60.0000 26

  3 omega   33.00   67.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000  -60.0000 34

  4 omega   50.00   98.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   57.0000  -60.0000 48

  5 omega   32.00  127.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   57.0000 -120.0000 95

  6 omega    2.00   78.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000  -57.0000  -90.0000 76

  7 omega  -11.00   80.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000  -57.0000   90.0000 91

  8 omega  136.00  175.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000 -150.0000 39

  9 omega   38.00  113.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -111.0000  150.0000 75

 10 omega   66.00   97.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -50.0000 -180.0000 31

 11 omega  130.00  164.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   50.0000   60.0000 34

 12 omega   81.00  131.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000 -150.0000 50

 13 omega   37.00   83.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -25.0000  120.0000 46

 14 omega   87.00  147.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   63.0000  150.0000 60

 15 omega  100.00  173.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  111.0000   60.0000 73

 16 omega   49.00   74.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -38.0000   30.0000 25

 17 omega  150.00  177.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  111.0000  150.0000 27

 18 omega   60.00  102.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -50.0000   60.0000 42

 19 omega   58.00   85.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -87.0000   95.0000 27

 20 omega   39.00   76.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -38.0000   90.0000 37

 21 omega   47.00   73.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -50.0000  -90.0000 26

 22 omega   74.00  104.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -50.0000  -90.0000 30

 23 omega   58.00   96.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -50.0000  120.0000 38

 24 omega  110.00  174.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  111.0000   90.0000 64

 25 omega   85.00  131.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   38.0000  -60.0000 46

 26 omega   45.00   70.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -25.0000   30.0000 25

 27 omega  122.00  175.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   63.0000 -120.0000 53

 28 omega  112.00  142.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  178.0000  -60.0000 30

 29 omega  117.00  143.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  111.0000  -30.0000 26
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0403252000
_diffrn_orient_matrix_UB_12      0.1119145000
_diffrn_orient_matrix_UB_13      -0.0283544000
_diffrn_orient_matrix_UB_21      -0.0959637000
_diffrn_orient_matrix_UB_22      -0.0553400000
_diffrn_orient_matrix_UB_23      -0.0432710000
_diffrn_orient_matrix_UB_31      -0.1580286000
_diffrn_orient_matrix_UB_32      0.0621835000
_diffrn_orient_matrix_UB_33      0.0125137000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0328
_diffrn_reflns_av_unetI/netI     0.0351
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            13153
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.500
_diffrn_reflns_theta_max         70.589
_diffrn_reflns_theta_min         5.037
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.863
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.46508
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_density_diffrn    1.587
_exptl_crystal_description       block
_exptl_crystal_F_000             1272
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.31
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.670
_refine_diff_density_min         -1.183
_refine_diff_density_rms         0.118
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.111
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     337
_refine_ls_number_reflns         4987
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.111
_refine_ls_R_factor_all          0.0397
_refine_ls_R_factor_gt           0.0386
_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^)+(0.0651P)^2^+0.8194P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1002
_refine_ls_wR_factor_ref         0.1016
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4777
_reflns_number_total             4987
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om500080z_si_003.cif
_cod_data_source_block           zhangll0628
_cod_depositor_comments
'Adding full bibliography for 4083051--4083052.cif.'
_cod_database_code               4083051
_reflns_odcompleteness_completeness 93.12
_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:
 C19(H19)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11), C13(H13),
 C14(H14), C16(H16), C17(H17), C23(H23), C24(H24), C26(H26), C27(H27)
2.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C)
;
_shelx_hkl_checksum              57715
_shelx_res_checksum              27542
_shelxl_version_number           2013-2