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_4514406
_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_formula_moiety         'C51 H47 I O2 P2 Pd, C H2 Cl2'
_chemical_formula_sum            'C52 H49 Cl2 I O2 P2 Pd'
_chemical_formula_weight         1072.05
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 115.788(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.6182(3)
_cell_length_b                   17.9333(2)
_cell_length_c                   12.3290(2)
_cell_measurement_reflns_used    38154
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      70.8190
_cell_measurement_theta_min      2.4750
_cell_volume                     2312.95(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.14d (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.14d (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.14d (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_temperature      150.15
_diffrn_measured_fraction_theta_full 0.982
_diffrn_measured_fraction_theta_max 0.970
_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    -88.00  88.00   1.00    1.00    --    0.00  20.00-150.00  176
  2  \w     76.00 101.00   1.00    1.00    --   16.00  60.00  17.39   25
  3  \w    -72.00 -14.00   1.00    1.00    --   16.00  60.00  17.39   58
  4  \w     21.00  47.00   1.00    1.00    --   16.00  60.00  17.39   26
  5  \w    -69.00 -13.00   1.00    1.00    --   20.00  60.00 153.24   56
  6  \w     42.00 109.00   1.00    1.00    --   20.00  60.00 153.24   67
  7  \w     26.00 109.00   1.00    1.00    --   20.00  60.00-103.16   83
  8  \w    -62.00  -8.00   1.00    1.00    --   20.00  60.00-103.16   54
  9  \w    -34.00   5.00   1.00    1.00    --   55.00  50.00  30.00   39
 10  \w    -33.00   6.00   1.00    1.00    --   56.00  58.00 124.73   39
 11  \w    -33.00   2.00   1.00    1.00    --   56.00  59.00 100.00   35
 12  \w    -33.00  -8.00   1.00    1.00    --   56.00  59.00-149.46   25
 13  \w    109.00 135.00   1.00    1.00    --   56.00  55.00 152.65   26
 14  \w    -33.00  -7.00   1.00    1.00    --   56.00  57.00 -39.00   26
 15  \w     73.00  99.00   1.00    1.00    --   56.00  57.00 -39.00   26
 16  \w    -32.00   3.00   1.00    1.00    --   56.00  57.00 -81.16   35
 17  \w    -32.00  16.00   1.00    1.00    --   56.00  55.00 152.65   48
 18  \w    -33.00  -7.00   1.00    1.00    --   56.00  58.00  -0.97   26
 19  \w      9.00  35.00   1.00    1.00    --   56.00  58.00  -0.97   26
 20  \w    -29.00   9.00   1.00    1.00    --   60.00  59.00  69.06   38
 21  \w    -29.00  -3.00   1.00    1.00    --   60.00  60.00-132.72   26
 22  \w     70.00  96.00   1.00    1.00    --   60.00  60.00  24.16   26
 23  \w    -29.00  12.00   1.00    1.00    --   60.00  58.00 162.05   41
 24  \w    -29.00  -3.00   1.00    1.00    --   60.00  59.00 -39.26   26
 25  \w    -29.00  -3.00   1.00    1.00    --   60.00  60.00  24.16   26
 26  \w    110.00 149.00   1.00    1.00    --   64.00  60.00-104.67   39
 27  \w    -25.00   1.00   1.00    1.00    --   64.00  60.00-104.67   26
 28  \w    -25.00  10.00   1.00    1.00    --   64.00  60.00  38.65   35
 29  \w     14.00  61.00   1.00    1.00    --   64.00  57.00 -23.93   47
 30  \w    -25.00  11.00   1.00    1.00    --   64.00  57.00 -23.93   36
 31  \w    -24.00  14.00   1.00    1.00    --   64.00  58.00 -74.54   38
 32  \w      9.00  54.00   1.00    1.00    --   64.00  59.00  70.77   45
 33  \w    -24.00   1.00   1.00    1.00    --   64.00  59.00  70.77   25
 34  \w    -22.00  88.00   1.00    1.00    --   64.00  58.00-162.60  110
 35  \w    -25.00   4.00   1.00    1.00    --   64.00  60.00-126.90   29
 36  \w    -21.00  73.00   1.00    1.00    --   68.00  60.00 -35.32   94
 37  \w     94.00 153.00   1.00    1.00    --   68.00  60.00 113.80   59
 38  \w     11.00  80.00   1.00    1.00    --   68.00  60.00 113.80   69
 39  \w    119.00 156.00   1.00    1.00    --   68.00  60.00 -35.32   37
 40  \w    -18.00   8.00   1.00    1.00    --   68.00  60.00 113.80   26
 41  \w    -21.00  88.00   1.00    1.00    --   68.00  57.00 174.23  109
 42  \w    124.00 156.00   1.00    1.00    --   68.00  58.00 165.38   32
 43  \w    -20.00   6.00   1.00    1.00    --   68.00  58.00 165.38   26
 44  \w    -13.00  70.00   1.00    1.00    --   76.00  58.00  87.96   83
 45  \w    129.00 164.00   1.00    1.00    --   76.00  57.00 121.10   35
 46  \w    -11.00  89.00   1.00    1.00    --   76.00  57.00 121.10  100
 47  \w    121.00 147.00   1.00    1.00    --   76.00  59.00   6.23   26
 48  \w    -13.00  70.00   1.00    1.00    --   76.00  59.00   6.23   83
 49  \w    131.00 165.00   1.00    1.00    --   76.00  59.00 -90.44   34
 50  \w    -13.00 124.00   1.00    1.00    --   76.00  59.00 -90.44  137
 51  \w     35.00 168.00   1.00    1.00    --   80.00  58.00-121.57  133
 52  \w     -9.00  24.00   1.00    1.00    --   80.00  58.00-121.57   33
 53  \w     -7.00  41.00   1.00    1.00    --   80.00  55.00 -93.74   48
 54  \w    132.00 157.00   1.00    1.00    --   80.00  55.00 -93.74   25
 55  \w     -9.00 168.00   1.00    1.00    --   80.00  59.00  33.87  177
 56  \w     23.00  50.00   1.00    1.00    --  110.00  40.00 120.00   27
 57  \w    117.00 192.00   1.00    1.00    --  110.00  40.00-150.00   75
 58  \w     21.00  49.00   1.00    1.00    --  110.00  40.00-150.00   28
 59  \w    112.00 174.00   1.00    1.00    --  110.00  40.00 -30.00   62
 60  \w     21.00  47.00   1.00    1.00    --  110.00  40.00 -30.00   26
 61  \w     22.00 197.00   1.00    1.00    --  110.00  40.00  60.00  175
 62  \w    142.00 197.00   1.00    1.00    --  110.00  40.00 120.00   55
 63  \w    151.00 183.00   1.00    1.00    --  110.00  40.00 150.00   32
 64  \w     74.00 100.00   1.00    1.00    --  110.00  40.00 150.00   26
 65  \w     21.00  50.00   1.00    1.00    --  110.00  40.00 150.00   29
 66  \w    147.00 177.00   1.00    1.00    --  110.00  40.00-120.00   30
 67  \w     21.00  47.00   1.00    1.00    --  110.00  40.00-120.00   26
 68  \w    152.00 191.00   1.00    1.00    --  110.00  40.00   0.00   39
 69  \w     21.00  48.00   1.00    1.00    --  110.00  40.00   0.00   27
 70  \w     21.00 121.00   1.00    1.00    --  110.00  30.00-180.00  100
 71  \w    112.00 145.00   1.00    1.00    --  110.00  30.00  90.00   33
 72  \w     21.00  76.00   1.00    1.00    --  110.00  30.00  90.00   55
 73  \w     21.00  47.00   1.00    1.00    --  110.00  30.00  60.00   26
 74  \w     21.00  99.00   1.00    1.00    --  110.00  20.00 -60.00   78
 75  \w     21.00 182.00   1.00    1.00    --  110.00  30.00 -30.00  161
 76  \w     22.00 143.00   1.00    1.00    --  110.00  20.00   0.00  121
 77  \w     21.00 189.00   1.00    1.00    --  110.00  30.00-120.00  168
 78  \w     21.00 105.00   1.00    1.00    --  110.00  30.00 120.00   84
 79  \w     22.00  94.00   1.00    1.00    --  110.00  30.00 -90.00   72
 80  \w     21.00  98.00   1.00    1.00    --  110.00  20.00 150.00   77
 81  \w     22.00  48.00   1.00    1.00    --  110.00  40.00-180.00   26
 82  \w    139.00 164.00   1.00    1.00    --  110.00  40.00  30.00   25
 83  \w     21.00  49.00   1.00    1.00    --  110.00  40.00  30.00   28
 84  \w     90.00 196.00   1.00    1.00    --  110.00  40.00  90.00  106
 85  \w     22.00  47.00   1.00    1.00    --  110.00  40.00  90.00   25
 86  \w    134.00 159.00   1.00    1.00    --  110.00  40.00 -60.00   25
 87  \w     21.00  47.00   1.00    1.00    --  110.00  40.00 -60.00   26
 88  \w     22.00 103.00   1.00    1.00    --  110.00  20.00-150.00   81
 89  \w     72.00  97.00   1.00    1.00    --  110.00  30.00  30.00   25
 90  \w     22.00  64.00   1.00    1.00    --  110.00  30.00  30.00   42
 91  \w    132.00 157.00   1.00    1.00    --  110.00  40.00 -90.00   25
 92  \w     21.00  47.00   1.00    1.00    --  110.00  40.00 -90.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0481
_diffrn_reflns_av_unetI/netI     0.0231
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            44218
_diffrn_reflns_point_group_measured_fraction_full 0.955
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.108
_diffrn_reflns_theta_min         4.226
_exptl_absorpt_coefficient_mu    10.502
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.05698
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.14d (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    1.539
_exptl_crystal_description       block
_exptl_crystal_F_000             1080
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.234
_refine_diff_density_min         -2.093
_refine_diff_density_rms         0.114
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.019(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     542
_refine_ls_number_reflns         8400
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0588
_refine_ls_R_factor_gt           0.0586
_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^)+(0.1204P)^2^+5.7141P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1576
_refine_ls_wR_factor_ref         0.1578
_reflns_Friedel_coverage         0.869
_reflns_Friedel_fraction_full    0.926
_reflns_Friedel_fraction_max     0.903
_reflns_number_gt                8320
_reflns_number_total             8400
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b00918_si_006.cif
_cod_data_source_block           s5299l
_cod_depositor_comments
'Adding full bibliography for 4514406--4514408.cif.'
_cod_database_code               4514406
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.420
_shelx_estimated_absorpt_t_min   0.179
_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 Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C21(H21A,
 H21B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C52(H52A,H52B)
2.b Aromatic/amide H refined with riding coordinates:
 C28(H28), C27(H27), C18(H18), C17(H17), C46(H46), C47(H47), C50(H50),
 C51(H51), C34(H34), C35(H35), C36(H36), C37(H37), C38(H38), C40(H40), C41(H41),
  C42(H42), C43(H43), C44(H44), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10),
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16)
2.c Idealised Me refined as rotating group:
 C49(H49A,H49B,H49C)
;
_shelx_res_checksum              98748
_shelx_hkl_checksum              81835
_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
;