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_4514781
_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         'C17 H11 Cr F O5'
_chemical_formula_sum            'C17 H11 Cr F O5'
_chemical_formula_weight         366.26
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-06-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.18 svn.r3508 for OlexSys, GUI svn.r5497)
;
_cell_angle_alpha                85.775(3)
_cell_angle_beta                 87.502(3)
_cell_angle_gamma                64.437(3)
_cell_formula_units_Z            2
_cell_length_a                   7.0791(2)
_cell_length_b                   7.2172(2)
_cell_length_c                   16.4881(6)
_cell_measurement_reflns_used    11673
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      76.5260
_cell_measurement_theta_min      6.9290
_cell_volume                     757.81(5)
_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 0.935
_diffrn_measured_fraction_theta_max 0.958
_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    -47.00  38.00   1.00    1.00    --  -44.80  64.00  73.00   85
  2  \w    -87.00  -9.00   1.00    1.00    --  -44.80 -64.00 -62.00   78
  3  \w   -153.00-126.00   1.00    1.00    -- -110.00 -64.00 -62.00   27
  4  \w   -106.00 -79.00   1.00    1.00    -- -110.00 -64.00 -62.00   27
  5  \w    -83.00 -42.00   1.00    1.00    -- -110.00  64.00  73.00   41
  6  \w   -140.00-113.00   1.00    1.00    -- -110.00  64.00  73.00   27
  7  \w    -23.00   4.00   1.00    1.00    --    5.00 -64.00 -62.00   27
  8  \w    -54.00 -27.00   1.00    1.00    --    5.00 -64.00 -62.00   27
  9  \w      8.00  33.00   1.00    1.00    --    5.00  64.00  73.00   25
 10  \w    -84.00  45.00   1.00    1.00    --  -44.80  76.00  90.00  129
 11  \w    -76.00  44.00   1.00    1.00    --  -44.80  57.00 -90.00  120
 12  \w   -151.00 -98.00   1.00    1.00    -- -110.00  38.00-180.00   53
 13  \w    -47.00 -22.00   1.00    1.00    -- -110.00  76.00 -60.00   25
 14  \w   -148.00 -25.00   1.00    1.00    -- -110.00  76.00   0.00  123
 15  \w   -131.00 -52.00   1.00    1.00    -- -110.00  76.00 -60.00   79
 16  \w    -66.00 -39.00   1.00    1.00    -- -110.00  76.00-150.00   27
 17  \w   -117.00 -22.00   1.00    1.00    -- -110.00  76.00 120.00   95
 18  \w    -99.00 -72.00   1.00    1.00    -- -110.00  76.00-150.00   27
 19  \w   -108.00 -21.00   1.00    1.00    -- -110.00  38.00 -30.00   87
 20  \w    -49.00 -23.00   1.00    1.00    -- -110.00  38.00-180.00   26
 21  \w   -151.00-125.00   1.00    1.00    -- -110.00  38.00 -30.00   26
 22  \w   -196.00 -27.00   1.00    1.00    -- -110.00  19.00-150.00  169
 23  \w   -113.00 -80.00   1.00    1.00    -- -110.00  76.00  60.00   33
 24  \w   -105.00 -69.00   1.00    1.00    -- -110.00  76.00-180.00   36
 25  \w    -53.00 -22.00   1.00    1.00    -- -110.00  76.00-180.00   31
 26  \w   -115.00 -21.00   1.00    1.00    -- -110.00  57.00-180.00   94
 27  \w    -66.00 -40.00   1.00    1.00    -- -110.00  57.00  60.00   26
 28  \w   -184.00-141.00   1.00    1.00    -- -110.00 -57.00-150.00   43
 29  \w   -103.00 -77.00   1.00    1.00    -- -110.00  64.00  73.00   26
 30  \w     16.00  43.00   1.00    1.00    --    5.00  57.00-180.00   27
 31  \w   -140.00-114.00   1.00    1.00    -- -110.00 -57.00-150.00   26
 32  \w   -119.00 -93.00   1.00    1.00    -- -110.00  57.00 -60.00   26
 33  \w    -96.00 -71.00   1.00    1.00    --  -45.00 -64.00 -62.00   25
 34  \w    -96.00 -71.00   1.00    1.00    --  -45.00 -64.00 -62.00   25
 35  \w   -176.00-136.00   1.00    1.00    -- -110.00 -64.00 -62.00   40
 36  \w   -127.00-100.00   1.00    1.00    -- -110.00 -57.00-180.00   27
 37  \w   -153.00-127.00   1.00    1.00    -- -110.00 -57.00-120.00   26
 38  \w    -99.00 -72.00   1.00    1.00    -- -110.00  76.00 150.00   27
 39  \w   -124.00 -97.00   1.00    1.00    -- -110.00  76.00  90.00   27
 40  \w   -168.00-142.00   1.00    1.00    -- -110.00 -57.00-180.00   26
 41  \w    -23.00   3.00   1.00    1.00    --    5.00  76.00-150.00   26
 42  \w     16.00  42.00   1.00    1.00    --    5.00  76.00-150.00   26
 43  \w    -37.00 -10.00   1.00    1.00    --  -45.00 -68.00  25.07   27
 44  \w   -134.00-104.00   1.00    1.00    --  -45.00 -68.00  25.07   30
 45  \w    -98.00 -72.00   1.00    1.00    --  -62.00 -74.00 126.02   26
 46  \w    -50.00 -24.00   1.00    1.00    --  -62.00 -72.00-132.86   26
 47  \w    -69.00 -23.00   1.00    1.00    --  -62.00 -74.00 126.02   46
 48  \w   -151.00-102.00   1.00    1.00    --  -62.00 -72.00-132.86   49
 49  \w    -47.00 -22.00   1.00    1.00    --  -62.00 -75.00 -39.86   25
 50  \w    -54.00 -27.00   1.00    1.00    --  -66.00 -74.00  43.59   27
 51  \w   -151.00-125.00   1.00    1.00    --  -66.00 -74.00  43.59   26
 52  \w    -70.00 -31.00   1.00    1.00    --  -70.00 -74.00-169.29   39
 53  \w   -152.00-126.00   1.00    1.00    --  -70.00 -74.00-169.29   26
 54  \w    -56.00 -30.00   1.00    1.00    --  -70.00 -75.00  12.08   26
 55  \w    -61.00 -34.00   1.00    1.00    --  -70.00 -68.00 -80.61   27
 56  \w    -65.00 -35.00   1.00    1.00    --  -74.00 -73.00  -5.98   30
 57  \w    -60.00 -34.00   1.00    1.00    --  -74.00 -75.00-100.55   26
 58  \w    -69.00 -39.00   1.00    1.00    --  -78.00 -74.00 150.38   30
 59  \w    -68.00 -43.00   1.00    1.00    --  -78.00 -69.00  79.51   25
 60  \w    -65.00 -39.00   1.00    1.00    --  -78.00 -73.00 -44.85   26
 61  \w   -138.00-112.00   1.00    1.00    --  -86.00 -72.00 131.37   26
 62  \w    -79.00 -48.00   1.00    1.00    --  -86.00 -72.00 131.37   31
 63  \w    -72.00 -46.00   1.00    1.00    --  -86.00 -76.00-112.85   26
 64  \w    -77.00 -51.00   1.00    1.00    --  -86.00 -69.00  59.44   26
 65  \w    -76.00 -46.00   1.00    1.00    --  -86.00 -75.00  99.28   30
 66  \w    -85.00 -50.00   1.00    1.00    --  -90.00 -76.00 -41.76   35
 67  \w   -120.00 -94.00   1.00    1.00    --  -90.00 -76.00 -41.76   26
 68  \w    -84.00 -51.00   1.00    1.00    --  -90.00 -76.00-151.91   33
 69  \w   -107.00 -58.00   1.00    1.00    --  -98.00 -76.00 -76.43   49
 70  \w   -107.00 -63.00   1.00    1.00    --  -98.00 -72.00-126.14   44
 71  \w   -125.00 -59.00   1.00    1.00    --  -98.00 -74.00 142.49   66
 72  \w   -105.00 -62.00   1.00    1.00    -- -102.00 -75.00 -15.38   43
 73  \w    -93.00 -62.00   1.00    1.00    -- -102.00 -76.00  20.98   31
 74  \w   -129.00-100.00   1.00    1.00    -- -102.00 -76.00  20.98   29
 75  \w    -93.00 -62.00   1.00    1.00    -- -102.00 -76.00  62.08   31
 76  \w   -150.00-113.00   1.00    1.00    -- -102.00 -76.00  62.08   37
 77  \w    -94.00 -64.00   1.00    1.00    -- -102.00 -72.00 107.23   30
 78  \w   -125.00 -63.00   1.00    1.00    -- -102.00 -75.00 -99.79   62
 79  \w    -97.00 -65.00   1.00    1.00    -- -102.00 -73.00-165.37   32
 80  \w   -166.00-126.00   1.00    1.00    -- -102.00 -73.00-165.37   40
 81  \w   -142.00-111.00   1.00    1.00    -- -102.00 -72.00 107.23   31
 82  \w   -102.00 -76.00   1.00    1.00    -- -110.00 -43.00 -63.98   26
 83  \w   -139.00-114.00   1.00    1.00    -- -110.00 -43.00 -63.98   25
 84  \w   -130.00 -70.00   1.00    1.00    -- -110.00 -76.00-175.64   60
 85  \w   -143.00 -70.00   1.00    1.00    -- -110.00 -76.00  98.24   73
 86  \w   -150.00 -71.00   1.00    1.00    -- -110.00 -75.00  43.43   79
;
_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      0.0518367000
_diffrn_orient_matrix_UB_12      0.1277486000
_diffrn_orient_matrix_UB_13      -0.0688051000
_diffrn_orient_matrix_UB_21      -0.2340834000
_diffrn_orient_matrix_UB_22      0.1486193000
_diffrn_orient_matrix_UB_23      -0.0067127000
_diffrn_orient_matrix_UB_31      0.0268624000
_diffrn_orient_matrix_UB_32      0.1333760000
_diffrn_orient_matrix_UB_33      0.0632451000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0188
_diffrn_reflns_av_unetI/netI     0.0153
_diffrn_reflns_Laue_measured_fraction_full 0.935
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            14891
_diffrn_reflns_point_group_measured_fraction_full 0.913
_diffrn_reflns_point_group_measured_fraction_max 0.935
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         66.594
_diffrn_reflns_theta_min         6.813
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    6.559
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54022
_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 yellowish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.605
_exptl_crystal_description       block
_exptl_crystal_F_000             372
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.329
_refine_diff_density_min         -0.453
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.018(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     455
_refine_ls_number_reflns         5014
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0484
_refine_ls_R_factor_gt           0.0479
_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^)+(0.1055P)^2^+0.2926P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1277
_refine_ls_wR_factor_ref         0.1284
_reflns_Friedel_coverage         0.953
_reflns_Friedel_fraction_full    0.891
_reflns_Friedel_fraction_max     0.913
_reflns_number_gt                4925
_reflns_number_total             5014
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b00918_si_004.cif
_cod_data_source_block           s5267r
_cod_original_cell_volume        757.81(4)
_cod_database_code               4514781
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.291
_shelx_estimated_absorpt_t_min   0.190
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(F2L)=Sof(H5A)=1-FVAR(1)
 Sof(H9A)=Sof(F2R)=FVAR(1)
 Sof(F1L)=Sof(H5)=1-FVAR(2)
 Sof(H9)=Sof(F1R)=FVAR(2)
3.a Aromatic/amide H refined with riding coordinates:
 C14A(H14A), C7(H7), C9A(H9A), C5A(H5A), C6A(H6A), C12A(H12A), C11A(H11A),
 C8A(H8A), C15A(H15A), C15(H15), C12(H12), C6(H6), C11(H11), C5(H5), C9(H9),
 C8(H8), C7A(H7A), C14(H14)
3.b Idealised Me refined as rotating group:
 C17(H17D,H17E,H17F), C17A(H17A,H17B,H17C)
;
_shelx_res_checksum              57930
_shelx_hkl_checksum              21560
_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 1.563
_oxdiff_exptl_absorpt_empirical_full_min 0.681