Catalytic Asymmetric C‒H Arylation of (η6-Arene)Chromium Complexes: Facile Access to Planar-Chiral Phosphines
Batuecas, María; Luo, Junfei; Gergelitsová, Ivana; Krämer, Katrina; Whitaker, Daniel; Vitorica-Yrezabal, Iñigo J.; Larrosa, Igor; ACS Catalysis 9 (2019) 5268–; doi:10.1021/acscatal.9b00918

data_4514407
_publ_section_title
;
 Catalytic Asymmetric C--H Arylation of (\h6-Arene)Chromium Complexes:
 Facile Access to Planar-Chiral Phosphines
;
_journal_issue                   6
_journal_name_full               'ACS Catalysis'
_journal_page_first              5268
_journal_paper_doi               10.1021/acscatal.9b00918
_journal_volume                  9
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C32 H24 Cr N O5 P, C5 H12'
_chemical_formula_sum            'C37 H36 Cr N O5 P'
_chemical_formula_weight         657.64
_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     dual
_audit_creation_date             2018-07-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.18 svn.r3508 for OlexSys, GUI svn.r5497)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.1500(3)
_cell_length_b                   19.5691(7)
_cell_length_c                   24.0399(11)
_cell_measurement_reflns_used    8014
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      72.9450
_cell_measurement_theta_min      2.9200
_cell_volume                     3363.6(2)
_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    '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      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.987
_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    -45.00 -20.00   1.00    2.00    --    5.00 -44.00   3.00   25
  2  \w    -50.00  35.00   1.00    2.00    --  -44.80  44.00 154.00   85
  3  \w   -119.00 -14.00   1.00    2.00    --  -44.80 -44.00   3.00  105
  4  \w   -183.00-146.00   1.00   10.00    -- -110.00 -44.00   3.00   37
  5  \w   -109.00 -82.00   1.00   10.00    -- -110.00 -44.00   3.00   27
  6  \w    -93.00 -47.00   1.00   10.00    -- -110.00  44.00 154.00   46
  7  \w      6.00  31.00   1.00    2.00    --    5.00  44.00 154.00   25
  8  \w    -39.00  36.00   1.00    2.00    --  -44.80  56.00-140.96   75
  9  \w    -91.00 -12.00   1.00    2.00    --  -44.80 -57.00 -90.00   79
 10  \w    -65.00 -28.00   1.00   10.00    -- -110.00  38.00   0.00   37
 11  \w    -98.00 -71.00   1.00   10.00    -- -110.00 -38.00-146.70   27
 12  \w    -99.00 -70.00   1.00   10.00    -- -110.00 -38.00 -60.00   29
 13  \w   -183.00-156.00   1.00   10.00    -- -110.00 -38.00-146.70   27
 14  \w   -193.00 -80.00   1.00   10.00    -- -110.00 -57.00-150.00  113
 15  \w   -100.00 -72.00   1.00   10.00    -- -110.00 -71.00 -84.51   28
 16  \w   -148.00 -21.00   1.00   10.00    -- -110.00  76.00 120.00  127
 17  \w   -106.00 -77.00   1.00   10.00    -- -110.00 -51.00-139.15   29
 18  \w   -150.00 -23.00   1.00   10.00    -- -110.00  76.00  60.00  127
 19  \w   -187.00-160.00   1.00   10.00    -- -110.00 -74.00-114.83   27
 20  \w    -97.00 -72.00   1.00   10.00    -- -110.00 -74.00-114.83   25
 21  \w    -95.00 -70.00   1.00   10.00    -- -110.00 -76.00 -90.00   25
 22  \w    -86.00 -22.00   1.00   10.00    -- -110.00  38.00 -60.00   64
 23  \w   -141.00 -69.00   1.00   10.00    -- -110.00 -33.00-168.07   72
 24  \w    -99.00 -72.00   1.00   10.00    -- -110.00 -44.00-115.07   27
 25  \w   -105.00 -71.00   1.00   10.00    -- -110.00 -41.00 -98.84   34
 26  \w    -98.00 -72.00   1.00   10.00    -- -110.00 -41.00 -68.81   26
 27  \w   -104.00 -78.00   1.00   10.00    -- -110.00  38.00 -90.00   26
 28  \w   -100.00 -73.00   1.00   10.00    -- -110.00 -47.00-119.46   27
 29  \w   -197.00 -82.00   1.00   10.00    -- -110.00 -35.00 -75.80  115
 30  \w   -152.00-125.00   1.00   10.00    -- -110.00 -49.00 -91.71   27
 31  \w   -100.00 -75.00   1.00   10.00    -- -110.00 -49.00 -91.71   25
 32  \w    -96.00 -71.00   1.00   10.00    -- -110.00 -43.00 -85.91   25
 33  \w   -100.00 -75.00   1.00   10.00    -- -110.00 -73.00 -73.42   25
 34  \w    -98.00 -73.00   1.00   10.00    -- -110.00 -47.00-141.30   25
 35  \w   -148.00 -86.00   1.00   10.00    -- -110.00  76.00 -90.00   62
 36  \w    -64.00 -28.00   1.00   10.00    -- -110.00  76.00 -90.00   36
 37  \w   -144.00-117.00   1.00   10.00    -- -110.00  38.00 -60.00   27
 38  \w    -95.00 -70.00   1.00   10.00    -- -110.00 -76.00 -60.00   25
 39  \w    -98.00 -73.00   1.00   10.00    -- -110.00 -47.00-122.35   25
 40  \w    -96.00 -71.00   1.00   10.00    -- -110.00 -43.00 -81.59   25
 41  \w    -94.00 -69.00   1.00   10.00    -- -110.00 -38.00-120.00   25
 42  \w   -198.00 -64.00   1.00   10.00    -- -110.00 -25.00-152.13  134
 43  \w   -101.00 -76.00   1.00   10.00    -- -110.00 -60.00-121.81   25
 44  \w   -102.00 -77.00   1.00   10.00    -- -110.00 -50.00-136.57   25
 45  \w   -100.00 -75.00   1.00   10.00    -- -110.00 -64.00 -99.61   25
 46  \w    -98.00 -73.00   1.00   10.00    -- -110.00 -47.00-115.56   25
 47  \w    -96.00 -71.00   1.00   10.00    -- -110.00 -41.00 -93.86   25
 48  \w    -82.00 -23.00   1.00   10.00    -- -110.00  76.00 -60.00   59
 49  \w   -141.00 -73.00   1.00   10.00    -- -110.00 -76.00 120.00   68
 50  \w    -95.00 -70.00   1.00   10.00    -- -110.00 -38.00-150.00   25
 51  \w   -173.00-148.00   1.00   10.00    -- -110.00 -38.00 -30.00   25
 52  \w    -97.00 -72.00   1.00   10.00    -- -110.00 -38.00 -30.00   25
 53  \w    -94.00 -69.00   1.00   10.00    -- -110.00 -38.00 -90.00   25
 54  \w    -48.00 -23.00   1.00   10.00    -- -110.00 -19.00-150.00   25
 55  \w   -143.00-115.00   1.00   10.00    -- -110.00  38.00   0.00   28
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0228376000
_diffrn_orient_matrix_UB_12      -0.0027446000
_diffrn_orient_matrix_UB_13      0.0636641000
_diffrn_orient_matrix_UB_21      -0.1171366000
_diffrn_orient_matrix_UB_22      -0.0656798000
_diffrn_orient_matrix_UB_23      -0.0055053000
_diffrn_orient_matrix_UB_31      0.1795100000
_diffrn_orient_matrix_UB_32      -0.0433014000
_diffrn_orient_matrix_UB_33      0.0044866000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0660
_diffrn_reflns_av_unetI/netI     0.0361
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            49228
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.677
_diffrn_reflns_theta_min         2.912
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    3.594
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74751
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.299
_exptl_crystal_description       plate
_exptl_crystal_F_000             1376
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.951
_refine_diff_density_min         -0.470
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Flack x determined using 2335 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.010(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     454
_refine_ls_number_reflns         7020
_refine_ls_number_restraints     102
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0689
_refine_ls_R_factor_gt           0.0590
_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^)+(0.0958P)^2^+1.7314P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1589
_refine_ls_wR_factor_ref         0.1690
_reflns_Friedel_coverage         0.753
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.972
_reflns_number_gt                6052
_reflns_number_total             7020
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b00918_si_005.cif
_cod_data_source_block           s5284r
_cod_depositor_comments
'Adding full bibliography for 4514406--4514408.cif.'
_cod_original_cell_volume        3363.7(2)
_cod_database_code               4514407
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         CrPC32H24NO5
_shelx_estimated_absorpt_t_max   0.813
_shelx_estimated_absorpt_t_min   0.467
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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. Restrained distances
 C36-C35 = C35-C34 = C34-C33 = C37-C33
 1.54 with sigma of 0.002
 C37A-C33A = C34A-C33A = C35A-C34A = C36A-C35A
 1.54 with sigma of 0.002
 C35-C33
 2.4 with sigma of 0.002
 C37A-C34A
 2.4 with sigma of 0.002
 C36-C34
 2.4 with sigma of 0.002
 C36A-C34A
 2.4 with sigma of 0.002
3. Uiso/Uaniso restraints and constraints
C34A \\sim C36A \\sim C35A \\sim C33A \\sim C37A: within 2A with sigma of 0.002
and sigma for terminal atoms of 0.004
C34 \\sim C33 \\sim C37 \\sim C35 \\sim C36: within 2A with sigma of 0.002 and
sigma for terminal atoms of 0.004
4. Rigid body (RIGU) restrains
 C33, C35, C34, C36, C37, C36A, C35A, C34A, C33A, C37A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=Sof(C35A)=Sof(H35C)=Sof(H35D)=
 Sof(C34A)=Sof(H34C)=Sof(H34D)=Sof(C33A)=Sof(H33C)=Sof(H33D)=Sof(C37A)=
 Sof(H37D)=Sof(H37E)=Sof(H37F)=1-FVAR(1)
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(C34)=Sof(H34A)=
 Sof(H34B)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C37)=Sof(H37A)=Sof(H37B)=
 Sof(H37C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C19(H19)
6.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C33(H33A,H33B), C35(H35A,
 H35B), C34(H34A,H34B), C35A(H35C,H35D), C34A(H34C,H34D), C33A(H33C,H33D)
6.c Me refined with riding coordinates:
 C36A(H36D,H36E,H36F), C37A(H37D,H37E,H37F)
6.d Aromatic/amide H refined with riding coordinates:
 C18(H18), C17(H17), C15(H15), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C9(H9),
 C10(H10), C11(H11), C12(H12), C13(H13), C24(H24), C25(H25), C28(H28), C29(H29)
6.e Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C37(H37A,H37B,H37C)
;
_shelx_res_checksum              5182
_shelx_hkl_checksum              21078
_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 1.620
_oxdiff_exptl_absorpt_empirical_full_min 0.574