The open d-shell enforces the active space in 3d metal catalysis: highly enantioselective chromium(ii) pincer catalysed hydrosilylation of ketones.
Schiwek, Christian H.; Vasilenko, Vladislav; Wadepohl, Hubert; Gade, Lutz H.; Chemical communications (Cambridge, England) 54 (2018) 9139–9142; doi:10.1039/c8cc05172k

data_7122024
_publ_section_title
;
 The open d-shell enforces the active space in 3d metal catalysis: highly
 enantioselective chromium(ii) pincer catalysed hydrosilylation of
 ketones.
;
_journal_issue                   66
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              9139
_journal_page_last               9142
_journal_paper_doi               10.1039/c8cc05172k
_journal_volume                  54
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H45 Cr N3 O2 Si'
_chemical_formula_sum            'C26 H45 Cr N3 O2 Si'
_chemical_formula_weight         511.74
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_chs2
_audit_creation_date             2018-02-16
_audit_creation_method
;
Olex2 1.2
(compiled Aug 10 2017 17:44:14 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-06-19 deposited with the CCDC.
2018-07-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.7996(7)
_cell_length_b                   14.2516(10)
_cell_length_c                   17.9837(12)
_cell_measurement_reflns_used    4672
_cell_measurement_temperature    220(1)
_cell_measurement_theta_max      20.5900
_cell_measurement_theta_min      2.5160
_cell_volume                     3024.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material
'encif (Wadepohl, 2009-17); encifer 1.5.2 (CCDC, 2016)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_environment      'perfluoro polyether oil / N~2~'
_diffrn_ambient_temperature      220(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.996
_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    -20.00  69.00   0.50   25.00    --   27.02 -99.00  60.00  178
  2  \w    -42.00  48.00   0.50   25.00    --   27.02 -57.00 120.00  180
  3  \w    -36.00  44.00   0.50   25.00    --   27.02 -57.00 -60.00  160
  4  \w     -3.00  97.00   0.50   25.00    --   27.02  77.00-180.00  200
  5  \w     -3.00  97.00   0.50   25.00    --   27.02  77.00 -30.00  200
  6  \w     -3.00  97.00   0.50   25.00    --   27.02  77.00  90.00  200
  7  \w    -20.00   8.00   0.50   25.00    --   27.02 -99.00 -90.00   56
  8  \w     35.00  69.00   0.50   25.00    --   27.02 -99.00 -90.00   68
  9  \w    -42.00  41.00   0.50   25.00    --   27.02 -57.00-150.00  166
 10  \w      7.00  96.00   0.50   25.00    --   27.02  57.00 -90.00  178
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0074033000
_diffrn_orient_matrix_UB_12      -0.0349146000
_diffrn_orient_matrix_UB_13      0.0275424000
_diffrn_orient_matrix_UB_21      0.0554218000
_diffrn_orient_matrix_UB_22      0.0092535000
_diffrn_orient_matrix_UB_23      0.0136596000
_diffrn_orient_matrix_UB_31      -0.0221722000
_diffrn_orient_matrix_UB_32      0.0341966000
_diffrn_orient_matrix_UB_33      0.0247075000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1452
_diffrn_reflns_av_unetI/netI     0.0775
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            38247
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.190
_diffrn_reflns_theta_max         25.190
_diffrn_reflns_theta_min         2.241
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.442
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.4110
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.124
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1104
_exptl_crystal_size_max          0.228
_exptl_crystal_size_mid          0.113
_exptl_crystal_size_min          0.044
_refine_diff_density_max         0.577
_refine_diff_density_min         -0.452
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 1128 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     309
_refine_ls_number_reflns         5422
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.1000
_refine_ls_R_factor_gt           0.0645
_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^)+(0.0767P)^2^+0.2349P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1553
_refine_ls_wR_factor_ref         0.1794
_reflns_Friedel_coverage         0.774
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                3677
_reflns_number_total             5422
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc05172k2.cif
_cod_data_source_block           ga_chs2
_cod_depositor_comments
'Adding full bibliography for 7122023--7122024.cif.'
_cod_database_code               7122024
_audit_block_refno               3047
_audit_block_usercomment         'chs59, irregular, yellow'
_shelx_estimated_absorpt_t_max   0.957
_shelx_estimated_absorpt_t_min   0.957
_reflns_odcompleteness_completeness 59.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_shelxl_version_number           2018/1
_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.a Ternary CH refined with riding coordinates:
 C1(H1), C12(H12), C13(H13), C16(H16)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C11(H11A,H11B), C23(H23A,H23B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7)
2.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,
 H22B,H22C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C)
;
_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
- B-factor correction
;
_shelx_res_checksum              37212
_cell_oxdiff_length_a            11.7924(5)
_cell_oxdiff_length_b            14.2605(6)
_cell_oxdiff_length_c            17.9839(8)
_cell_oxdiff_angle_alpha         90.282(3)
_cell_oxdiff_angle_beta          90.127(4)
_cell_oxdiff_angle_gamma         90.251(4)
_cell_oxdiff_volume              3024.2(2)
_cell_oxdiff_measurement_reflns_used 4672