Cobalt-Catalyzed Hydrogenations via Olefin Cobaltate and Hydride Intermediates
Sandl, Sebastian; Maier, Thomas M.; van Leest, Nicolaas P.; Kröncke, Susanne; Chakraborty, Uttam; Demeshko, Serhiy; Koszinowski, Konrad; de Bruin, Bas; Meyer, Franc; Bodensteiner, Michael; Herrmann, Carmen; Wolf, Robert; Jacobi von Wangelin, Axel; ACS Catalysis 9 (2019) 7596–; doi:10.1021/acscatal.9b01584

data_4514644
_publ_section_title
;
 Cobalt-Catalyzed Hydrogenations via Olefin Cobaltate and Hydride
 Intermediates
;
_journal_issue                   8
_journal_name_full               'ACS Catalysis'
_journal_page_first              7596
_journal_paper_doi               10.1021/acscatal.9b01584
_journal_volume                  9
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C48 H60 Co Li N2 O'
_chemical_formula_sum            'C48 H60 Co Li N2 O'
_chemical_formula_weight         746.85
_space_group_crystal_system      orthorhombic
_space_group_IT_number           31
_space_group_name_Hall           'P 2ac -2'
_space_group_name_H-M_alt        'P m n 21'
_symmetry_space_group_name_Hall  'P 2ac -2'
_symmetry_space_group_name_H-M   'P m n 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-08-16
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   17.4715(2)
_cell_length_b                   10.54720(10)
_cell_length_c                   10.97630(10)
_cell_measurement_reflns_used    9806
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      73.1010
_cell_measurement_theta_min      4.7310
_cell_volume                     2022.66(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.37b (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.37b (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.37b (Rigaku OD, 2017)'
_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      N~2~
_diffrn_ambient_temperature      123.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 4.2047
_diffrn_detector_type            TitanS2
_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     17.00 113.00   1.00    2.00    --   44.10  77.00 120.00   96
  2  \w    119.00 151.00   1.00    8.00    --  104.50  61.00 150.00   32
  3  \w     73.00 167.00   1.00    8.00    --  104.50 125.00 -30.00   94
  4  \w    145.00 177.00   1.00    8.00    --  104.50 125.00 -90.00   32
  5  \w    101.00 157.00   1.00    8.00    --  104.50  69.00-102.00   56
  6  \w     96.00 146.00   1.00    8.00    --  104.50  45.00-120.00   50
  7  \w     92.00 118.00   1.00    8.00    --  104.50 -30.00 -60.00   26
  8  \w     66.00 131.00   1.00    8.00    --  104.50 -77.00 -60.00   65
  9  \w     86.00 114.00   1.00    8.00    --  104.50-125.00 -30.00   28
 10  \w     46.00 129.00   1.00    8.00    --  104.50 -61.00-150.00   83
 11  \w     80.00 106.00   1.00    8.00    --  104.50 -94.00-180.00   26
 12  \w     38.00  81.00   1.00    8.00    --  104.50 -30.00 -60.00   43
 13  \w     38.00 126.00   1.00    8.00    --  104.50 -45.00  60.00   88
 14  \w     32.00 121.00   1.00    8.00    --  104.50-125.00 120.00   89
 15  \w     34.00  59.00   1.00    8.00    --  104.50-125.00 -30.00   25
 16  \w    -22.00  71.00   1.00    2.00    --   44.10 -77.00   0.00   93
 17  \w    -25.00  63.00   1.00    2.00    --   44.10 -57.00-150.00   88
 18  \w     73.00 121.00   1.00    8.00    --  104.50 125.00 -90.00   48
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'GV50, TitanS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0674788000
_diffrn_orient_matrix_UB_12      0.0384996000
_diffrn_orient_matrix_UB_13      0.0823446000
_diffrn_orient_matrix_UB_21      0.0129637000
_diffrn_orient_matrix_UB_22      -0.1400841000
_diffrn_orient_matrix_UB_23      0.0339422000
_diffrn_orient_matrix_UB_31      0.0553037000
_diffrn_orient_matrix_UB_32      -0.0144789000
_diffrn_orient_matrix_UB_33      -0.1084945000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0328
_diffrn_reflns_av_unetI/netI     0.0300
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            14345
_diffrn_reflns_point_group_measured_fraction_full 0.921
_diffrn_reflns_point_group_measured_fraction_max 0.905
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.654
_diffrn_reflns_theta_min         4.192
_diffrn_source                   'gradient vaccum rotating-anode X-ray tube'
_diffrn_source_type              'GV1000 (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.600
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.514
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.37b (Rigaku Oxford Diffraction, 2017)
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            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.226
_exptl_crystal_description       plate
_exptl_crystal_F_000             800
_exptl_crystal_size_max          0.346
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.093
_refine_diff_density_max         0.197
_refine_diff_density_min         -0.414
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 1506 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.021(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     286
_refine_ls_number_reflns         3823
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0317
_refine_ls_R_factor_gt           0.0307
_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^)+(0.0554P)^2^+0.2600P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0791
_refine_ls_wR_factor_ref         0.0801
_reflns_Friedel_coverage         0.732
_reflns_Friedel_fraction_full    0.833
_reflns_Friedel_fraction_max     0.810
_reflns_number_gt                3744
_reflns_number_total             3823
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b01584_si_002.cif
_cod_data_source_block           op_neu
_cod_database_code               4514644
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C98  H124  Co2  Li2  N4  O2  '
_shelx_estimated_absorpt_t_max   0.731
_shelx_estimated_absorpt_t_min   0.369
_reflns_odcompleteness_completeness 99.95
_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 C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(C23A)=Sof(H23C)=Sof(H23D)=1-FVAR(1)
 Sof(C23)=Sof(H23A)=Sof(H23B)=FVAR(1)
 Sof(C20A)=Sof(H20C)=Sof(H20D)=1-FVAR(2)
 Sof(C20)=Sof(H20A)=Sof(H20B)=FVAR(2)
 Fixed Sof: C25(0.5) H25A(0.5) H25B(0.5) C27(0.5) H27A(0.5) H27B(0.5) C26(0.5)
 H26A(0.5) H26B(0.5) H24A(0.5) H24B(0.5)
3.a Ternary CH refined with riding coordinates:
 C14(H14), C21(H21), C22(H22), C17(H17)
3.b Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C20(H20A,H20B), C23A(H23C,H23D), C20A(H20C,H20D), C25(H25A,
 H25B), C27(H27A,H27B), C26(H26A,H26B), C24(H24A,H24B)
3.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C11(H11), C3(H3), C10(H10), C4(H4), C5(H5)
3.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C19(H19A,H19B,H19C), C15(H15A,H15B,H15C), C18(H18A,H18B,
 H18C)
;
_shelx_res_checksum              53867
_shelx_hkl_checksum              8598
_olex2_diffrn_ambient_temperature_device 'CryoStream 700'
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.240
_oxdiff_exptl_absorpt_empirical_full_min 0.768