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_7122023
_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         'C22 H34 Cl Cr N3 O2'
_chemical_formula_sum            'C22 H34 Cl Cr N3 O2'
_chemical_formula_weight         459.97
_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_chs1
_audit_creation_date             2017-12-01
_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                   9.01882(13)
_cell_length_b                   13.64803(16)
_cell_length_c                   19.2371(2)
_cell_measurement_reflns_used    48262
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      31.5770
_cell_measurement_theta_min      2.5890
_cell_volume                     2367.88(5)
_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      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_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    -43.00  57.00   0.50   10.00    --   26.87 -77.00  90.00  200
  2  \w    -20.00  69.00   0.50   10.00    --   26.87 -99.00 -90.00  178
  3  \w    -42.00  48.00   0.50   10.00    --   26.87 -57.00 -30.00  180
  4  \w      6.00  96.00   0.50   10.00    --   26.87  57.00 -60.00  180
  5  \w    -42.00  48.00   0.50   10.00    --   26.87 -57.00 150.00  180
  6  \w     -3.00  97.00   0.50   10.00    --   26.87  77.00  30.00  200
  7  \w     -3.00  97.00   0.50   10.00    --   26.87  77.00-180.00  200
  8  \w      6.00  96.00   0.50   10.00    --   26.87  57.00 120.00  180
  9  \w      6.00  96.00   0.50   10.00    --   26.87  57.00   0.00  180
 10  \w    -20.00  69.00   0.50   10.00    --   26.87 -99.00 -60.00  178
 11  \w     -3.00  97.00   0.50   10.00    --   26.87  77.00-120.00  200
 12  \w    -19.00  69.00   0.50   10.00    --   26.87-100.00-145.00  176
 13  \w      1.00  99.00   0.50   10.00    --   26.87  38.00 150.00  196
 14  \w    -20.00  69.00   0.50   10.00    --   26.87 -99.00  60.00  178
 15  \w      1.00  99.00   0.50   10.00    --   26.87  38.00   0.00  196
 16  \w     -3.00  97.00   0.50   10.00    --   26.87  77.00 -90.00  200
 17  \w    -20.00  69.00   0.50   10.00    --   26.87 -99.00-180.00  178
 18  \w    -20.00  69.00   0.50   10.00    --   26.87 -99.00 -30.00  178
 19  \w      6.00  96.00   0.50   10.00    --   26.87  57.00-150.00  180
 20  \w     -3.00  97.00   0.50   10.00    --   26.87  77.00 150.00  200
 21  \f      0.00 120.00   0.50   10.00  26.87  26.87  40.00    --   240
 22  \f      0.00 120.00   0.50   10.00  26.87  26.87 -60.00    --   240
 23  \f      0.00 120.00   0.50   10.00  26.87  26.87  60.00    --   240
 24  \f    120.00 240.00   0.50   10.00  26.87  26.87 -40.00    --   240
 25  \f    120.00 240.00   0.50   10.00  26.87  26.87  40.00    --   240
 26  \f      0.00 120.00   0.50   10.00  26.87  26.87 -40.00    --   240
 27  \f    120.00 240.00   0.50   10.00  26.87  26.87  60.00    --   240
 28  \f    240.00 360.00   0.50   10.00  26.87  26.87 -40.00    --   240
 29  \f    240.00 360.00   0.50   10.00  26.87  26.87  40.00    --   240
 30  \f    240.00 360.00   0.50   10.00  26.87  26.87 -60.00    --   240
 31  \f    240.00 360.00   0.50   10.00  26.87  26.87  60.00    --   240
 32  \f    120.00 240.00   0.50   10.00  26.87  26.87 -60.00    --   240
 33  \w     -3.00  22.00   0.50   10.00    --   26.87  77.00-150.00   50
 34  \w     -3.00  97.00   0.50   10.00    --   26.87  77.00-180.00  200
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0611260000
_diffrn_orient_matrix_UB_12      0.0327039000
_diffrn_orient_matrix_UB_13      0.0015677000
_diffrn_orient_matrix_UB_21      -0.0179456000
_diffrn_orient_matrix_UB_22      0.0113454000
_diffrn_orient_matrix_UB_23      0.0349735000
_diffrn_orient_matrix_UB_31      0.0461208000
_diffrn_orient_matrix_UB_32      -0.0387730000
_diffrn_orient_matrix_UB_33      0.0115554000
_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  0.0691
_diffrn_reflns_av_unetI/netI     0.0273
_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       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            193770
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.365
_diffrn_reflns_theta_min         2.117
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.618
_exptl_absorpt_correction_T_max  1.116
_exptl_absorpt_correction_T_min  0.911
_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            bronze
_exptl_crystal_density_diffrn    1.290
_exptl_crystal_description       irregular
_exptl_crystal_F_000             976
_exptl_crystal_size_max          0.199
_exptl_crystal_size_mid          0.153
_exptl_crystal_size_min          0.100
_refine_diff_density_max         0.502
_refine_diff_density_min         -0.232
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Flack x determined using 3048 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.019(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     270
_refine_ls_number_reflns         8348
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0449
_refine_ls_R_factor_gt           0.0378
_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^)+(0.0508P)^2^+0.6211P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0912
_refine_ls_wR_factor_ref         0.0946
_reflns_Friedel_coverage         0.784
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.977
_reflns_number_gt                7583
_reflns_number_total             8348
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc05172k2.cif
_cod_data_source_block           ga_chs1
_cod_depositor_comments
'Adding full bibliography for 7122023--7122024.cif.'
_cod_database_code               7122023
_audit_block_refno               2992
_audit_block_usercomment         'chs53, irregular, bronze'
_chemical_oxdiff_formula         'C22 H34 Cl Cr N3 O2'
_chemical_oxdiff_usercomment     'chs53, irregular, bronze'
_shelx_estimated_absorpt_t_max   0.941
_shelx_estimated_absorpt_t_min   0.941
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_shelxl_version_number           2017/1
_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)
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)
;
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.125
_oxdiff_exptl_absorpt_empirical_full_min 0.900
_shelx_res_checksum              13359
_cell_oxdiff_length_a            9.01864(12)
_cell_oxdiff_length_b            13.64648(18)
_cell_oxdiff_length_c            19.2397(2)
_cell_oxdiff_angle_alpha         90.0007(10)
_cell_oxdiff_angle_beta          90.0228(10)
_cell_oxdiff_angle_gamma         90.1013(11)
_cell_oxdiff_volume              2367.88(5)
_cell_oxdiff_measurement_reflns_used 48262