Chiral Cyclopentadienyl Cobalt(III) Complexes Enable Highly Enantioselective 3d-Metal-Catalyzed C-H Functionalizations.
Ozols, Kristers; Jang, Yun-Suk; Cramer, Nicolai; Journal of the American Chemical Society 141 (2019) 5675–5680; doi:10.1021/jacs.9b02569

data_4128401
_publ_section_title
;
 Chiral Cyclopentadienyl Cobalt(III) Complexes Enable Highly
 Enantioselective 3d-Metal-Catalyzed C-H Functionalizations.
;
_journal_issue                   14
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5675
_journal_page_last               5680
_journal_paper_doi               10.1021/jacs.9b02569
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C12 H13 N O3'
_chemical_formula_sum            'C12 H13 N O3'
_chemical_formula_weight         219.23
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2018/3
_cell_angle_alpha                90
_cell_angle_beta                 101.4250(19)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.8622(2)
_cell_length_b                   5.17605(11)
_cell_length_c                   19.4320(4)
_cell_measurement_reflns_used    8119
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      73.4680
_cell_measurement_theta_min      4.0930
_cell_volume                     1070.88(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Mercury 4.0.0 (CCDC, 2018)'
_computing_publication_material  'CIFTab (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      140.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_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   -116.00 -90.00   1.00    1.00    --  -43.01 -37.00 -30.00   26
  2  \w    -42.00 -15.00   1.00    1.00    --  -43.01 -57.00 150.00   27
  3  \w    -68.00  30.00   1.00    1.00    --  -43.01  57.00 -60.00   98
  4  \w   -104.00 -78.00   1.00    1.00    --  -43.01 -57.00 150.00   26
  5  \w    -43.00 -15.00   1.00    1.00    --  -43.01 -57.00 -90.00   28
  6  \w   -123.00 -80.00   1.00    1.00    --  -43.01 -99.00-120.00   43
  7  \w    -79.00 -21.00   1.00    1.00    --  -43.01 -37.00 -30.00   58
  8  \w   -109.00 -72.00   1.00    1.00    --  -43.01 -57.00 -90.00   37
  9  \w     27.00  99.00   1.00    1.00    --   43.01-125.00  90.00   72
 10  \w     12.00  38.00   1.00    1.00    --   46.00  84.00 -88.39   26
 11  \w     12.00  37.00   1.00    1.00    --   46.00  83.00  96.84   25
 12  \w     12.00  45.00   1.00    1.00    --   46.00  82.00 165.84   33
 13  \w     20.00  45.00   1.00    1.00    --   50.00  80.00-152.06   25
 14  \w     16.00  41.00   1.00    1.00    --   50.00  81.00  14.21   25
 15  \w     17.00  44.00   1.00    1.00    --   50.00  80.00 -54.22   27
 16  \w     31.00  61.00   1.00    1.00    --   62.00  77.00  -0.98   30
 17  \w     29.00  55.00   1.00    1.00    --   62.00  77.00  48.25   26
 18  \w     30.00  65.00   1.00    1.00    --   62.00  76.00 101.04   35
 19  \w     33.00  96.00   1.00    1.00    --   62.00  74.00-126.00   63
 20  \w     34.00  60.00   1.00    1.00    --   66.00  76.00 121.31   26
 21  \w     76.00 101.00   1.00    1.00    --   66.00  76.00 121.31   25
 22  \w     34.00  61.00   1.00    1.00    --   66.00  77.00 143.78   27
 23  \w    108.00 146.00   1.00    1.00    --   70.00  76.00 -37.96   38
 24  \w     38.00  75.00   1.00    1.00    --   70.00  76.00 -37.96   37
 25  \w     41.00  68.00   1.00    1.00    --   70.00  70.00   1.98   27
 26  \w     39.00  64.00   1.00    1.00    --   70.00  70.00  31.66   25
 27  \w     40.00  74.00   1.00    1.00    --   70.00  77.00 174.26   34
 28  \w     41.00  75.00   1.00    1.00    --   74.00  77.00  55.25   34
 29  \w    104.00 144.00   1.00    4.00    --   78.00  76.00 -77.22   40
 30  \w     46.00  89.00   1.00    4.00    --   78.00  76.00 -77.22   43
 31  \w     56.00  82.00   1.00    4.00    --   86.00  64.00 -14.65   26
 32  \w     55.00 110.00   1.00    4.00    --   86.00  74.00 117.75   55
 33  \w     73.00 178.00   1.00    4.00    --  105.68  77.00  60.00  105
 34  \w     40.00  66.00   1.00    4.00    --  105.68-125.00 -60.00   26
 35  \w     73.00 110.00   1.00    4.00    --  105.68  77.00 -60.00   37
 36  \w     33.00 105.00   1.00    4.00    --  105.68 -94.00  30.00   72
 37  \w     74.00 177.00   1.00    4.00    --  105.68  76.00 175.39  103
 38  \w     78.00 104.00   1.00    4.00    --  105.68  61.00 150.00   26
 39  \w     73.00 168.00   1.00    4.00    --  105.68  77.00-150.00   95
 40  \w     73.00 142.00   1.00    4.00    --  105.68  77.00  30.00   69
 41  \w     74.00 118.00   1.00    4.00    --  105.68-125.00-150.00   44
 42  \w     79.00 105.00   1.00    4.00    --  105.68  61.00  30.00   26
 43  \w    113.00 171.00   1.00    4.00    --  105.68  77.00 120.00   58
 44  \w     77.00 165.00   1.00    4.00    --  105.68  77.00 -90.00   88
 45  \w     76.00 103.00   1.00    4.00    --  105.68  77.00 120.00   27
 46  \w    114.00 140.00   1.00    4.00    --  105.68  77.00 -30.00   26
 47  \w     73.00 102.00   1.00    4.00    --  105.68  77.00 -30.00   29
 48  \w     33.00 131.00   1.00    4.00    --  105.68 -45.00 120.00   98
 49  \w     73.00 137.00   1.00    4.00    --  105.68  77.00-120.00   64
 50  \w     77.00 104.00   1.00    4.00    --  105.68  61.00-150.00   27
 51  \w    111.00 149.00   1.00    4.00    --  105.68  77.00  90.00   38
 52  \w     74.00 105.00   1.00    4.00    --  105.68  77.00  90.00   31
 53  \w     63.00  98.00   1.00    4.00    --  105.68 -94.00 -30.00   35
 54  \w     75.00 100.00   1.00    4.00    --  105.68  77.00   0.00   25
 55  \w     33.00  59.00   1.00    4.00    --  105.68 -94.00 -30.00   26
 56  \w     79.00 144.00   1.00    4.00    --  105.68  61.00   0.00   65
 57  \w     73.00 141.00   1.00    4.00    --  105.68  77.00 150.00   68
 58  \w    114.00 140.00   1.00    4.00    --  105.68  77.00 -60.00   26
 59  \w     23.00  84.00   1.00    4.00    --  105.68 -94.00 120.00   61
 60  \w     67.00 118.00   1.00    4.00    --  105.68-125.00 -60.00   51
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0398
_diffrn_reflns_av_unetI/netI     0.0291
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            18179
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.792
_diffrn_reflns_theta_min         4.152
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.811
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.466
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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            'clear light colourless'
_exptl_crystal_density_diffrn    1.360
_exptl_crystal_description       needle
_exptl_crystal_F_000             464
_exptl_crystal_size_max          0.951
_exptl_crystal_size_mid          0.098
_exptl_crystal_size_min          0.077
_refine_diff_density_max         0.321
_refine_diff_density_min         -0.183
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.2(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     300
_refine_ls_number_reflns         4155
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.0412
_refine_ls_R_factor_gt           0.0372
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0557P)^2^+0.1944P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0933
_refine_ls_wR_factor_ref         0.0970
_reflns_Friedel_coverage         0.733
_reflns_Friedel_fraction_full    0.954
_reflns_Friedel_fraction_max     0.917
_reflns_number_gt                3864
_reflns_number_total             4155
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b02569_si_008.cif
_cod_data_source_block           koz-1-545
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4128401
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.512
_shelx_estimated_absorpt_t_max   0.940
_shelx_res_checksum              18681
_shelx_hkl_checksum              5101