Heterocyclic Suzuki-Miyaura coupling reaction of metalla-aromatics and mechanistic analysis of site selectivity.
Lin, Zuzhang; Cai, Yapeng; Zhang, Yaowei; Zhang, Hong; Xia, Haiping; Chemical science 14 (2023) 1227–1233; doi:10.1039/d2sc05455h

data_1568212
_publ_section_title
;
 Heterocyclic Suzuki-Miyaura coupling reaction of metalla-aromatics and
 mechanistic analysis of site selectivity.
;
_journal_issue                   5
_journal_name_full               'Chemical science'
_journal_page_first              1227
_journal_page_last               1233
_journal_paper_doi               10.1039/d2sc05455h
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C84 H65 Br Os P3, C2 H4 Cl2, Br'
_chemical_formula_sum            'C86 H69 Br Cl3 Os P3'
_chemical_formula_weight         1571.78
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-06-13
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-08-05 deposited with the CCDC.	2022-12-30 downloaded from the CCDC.
;
_cell_angle_alpha                93.513(2)
_cell_angle_beta                 96.836(2)
_cell_angle_gamma                101.444(2)
_cell_formula_units_Z            2
_cell_length_a                   13.8929(3)
_cell_length_b                   15.2075(3)
_cell_length_c                   18.0219(4)
_cell_measurement_reflns_used    30665
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.7870
_cell_measurement_theta_min      2.4900
_cell_volume                     3691.25(14)
_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 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.991
_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     27.00  53.00   0.50    0.50    --   52.00  79.00 -81.01   52
  2  \w     36.00  69.00   0.50    0.50    --   60.00  77.00 -78.54   66
  3  \w     73.00 124.00   0.50    0.50    --   52.00  79.00 -81.01  102
  4  \w    104.00 130.00   0.50    0.50    --   60.00  77.00 -78.54   52
  5  \w    102.00 174.00   0.50    1.20    --  105.73 109.00 -92.00  144
  6  \w     81.00 132.00   0.50    0.50    --   60.00  78.00 122.85  102
  7  \w     62.00 122.00   0.50    0.50    --   52.00  83.00 -20.32  120
  8  \w     39.00  74.00   0.50    0.50    --   64.00  79.00-146.63   70
  9  \w     44.00  74.00   0.50    0.50    --   68.00  78.00 -70.25   60
 10  \w     45.00  72.00   0.50    0.50    --   68.00  76.00  -2.64   54
 11  \w     31.00  63.00   0.50    0.50    --   56.00  79.00  54.85   64
 12  \w     20.00  45.00   0.50    0.50    --   48.00  87.00  16.23   50
 13  \w     26.00  59.00   0.50    0.50    --   52.00  83.00 -20.32   66
 14  \w     19.00  44.00   0.50    0.50    --   48.00  88.00 -46.85   50
 15  \w     19.00  46.00   0.50    0.50    --   48.00  88.00-101.18   54
 16  \w     20.00  45.00   0.50    0.50    --   48.00  86.00-124.96   50
 17  \w      9.00  34.00   0.50    0.50    --   40.00  93.00-164.97   50
 18  \w     -2.00  24.00   0.50    0.50    --   32.00  99.00-123.00   52
 19  \w    -22.00   3.00   0.50    0.50    --   16.00 106.00 -63.80   50
 20  \w     -3.00  30.00   0.50    0.50    --   28.00  96.00 -30.62   66
 21  \w    -19.00  10.00   0.50    0.50    --   16.00 103.00  25.68   58
 22  \w      8.00  36.00   0.50    0.50    --   40.00  94.00  81.33   56
 23  \w     17.00  42.00   0.50    0.50    --   48.00  92.00  75.15   50
 24  \w     31.00  72.00   0.50    0.50    --   56.00  80.00 111.76   82
 25  \w     35.00  68.00   0.50    0.50    --   60.00  79.00 157.58   66
 26  \w     36.00  63.00   0.50    0.50    --   60.00  78.00 122.85   54
 27  \w     19.00  44.00   0.50    0.50    --   48.00  88.00 159.14   50
 28  \w    -23.00   2.00   0.50    0.50    --   16.00 110.00 165.67   50
 29  \w    -51.00 -21.00   0.50    0.50    --    0.00 132.00  16.83   60
 30  \w    -84.00   1.00   0.50    0.50    --  -46.81 109.00 -92.00  170
 31  \w    -18.00  61.00   0.50    0.50    --   46.81 -57.00-150.00  158
 32  \w     81.00 116.00   0.50    1.20    --  105.73-125.00 -60.00   70
 33  \w     78.00 105.00   0.50    1.20    --  105.73 -94.00   0.00   54
 34  \w     40.00 121.00   0.50    1.20    --  105.73 -77.00 -30.00  162
 35  \w     46.00 120.00   0.50    1.20    --  105.73 -30.00 150.00  148
 36  \w     34.00  65.00   0.50    1.20    --  105.73 -94.00   0.00   62
 37  \w     34.00  61.00   0.50    1.20    --  105.73-125.00 -60.00   54
 38  \w     33.00 118.00   0.50    1.20    --  105.73 -61.00 -30.00  170
 39  \w     33.00  59.00   0.50    1.20    --  105.73 -94.00 120.00   52
 40  \w     19.00  73.00   0.50    0.50    --   46.81-109.00 171.00  108
 41  \w    -54.00 -25.00   0.50    0.50    --  -52.00 -83.00 162.40   58
 42  \w    -68.00 -42.00   0.50    1.20    --  -68.00 -82.00  54.63   52
 43  \w    -62.00 -37.00   0.50    0.50    --  -60.00 -74.00  -6.73   50
 44  \w    -68.00 -38.00   0.50    0.50    --  -60.00 -73.00 -44.32   60
 45  \w    -65.00 -37.00   0.50    0.50    --  -60.00 -75.00 -74.91   56
 46  \w    -70.00 -42.00   0.50    1.20    --  -68.00 -83.00 -69.20   56
 47  \w    -72.00 -46.00   0.50    1.20    --  -72.00 -82.00 -97.39   52
 48  \w    -76.00 -41.00   0.50    1.20    --  -68.00 -83.00-132.02   70
 49  \w    -77.00 -50.00   0.50    1.20    --  -76.00 -82.00-158.26   54
 50  \w    -87.00 -57.00   0.50    1.20    --  -80.00 -75.00 -76.14   60
 51  \w    -77.00 -50.00   0.50    1.20    --  -76.00 -82.00 -35.76   54
 52  \w    -72.00 -45.00   0.50    1.20    --  -72.00 -83.00  10.68   54
 53  \w    -80.00 -45.00   0.50    1.20    --  -72.00 -83.00  32.92   70
 54  \w    -76.00 -49.00   0.50    1.20    --  -76.00 -83.00 122.32   54
 55  \w    -70.00 -43.00   0.50    1.20    --  -68.00 -82.00 176.70   54
 56  \w    -85.00 -49.00   0.50    1.20    --  -76.00 -83.00 160.43   72
 57  \w    -97.00 -56.00   0.50    0.50    --  -52.00 -83.00 162.40   82
 58  \w    -89.00 -61.00   0.50    1.20    --  -84.00 -74.00 138.43   56
 59  \w    -90.00 -63.00   0.50    1.20    --  -88.50 -80.00 176.51   54
 60  \w   -102.00 -66.00   0.50    1.20    --  -88.50 -73.00  45.57   72
 61  \w    -97.00 -63.00   0.50    1.20    --  -88.50 -81.00  -0.37   68
 62  \w    -79.00 -53.00   0.50    1.20    --  -76.00 -74.00 -30.37   52
 63  \w    -88.00 -62.00   0.50    1.20    --  -84.00 -72.00-102.76   52
 64  \w    -88.00 -63.00   0.50    1.20    --  -88.50 -81.00 -95.37   50
 65  \w    -92.00 -65.00   0.50    1.20    --  -88.50 -77.00-150.00   54
 66  \w   -102.00 -36.00   0.50    0.50    --  -46.81 -37.00-150.00  132
 67  \w   -101.00 -64.00   0.50    1.20    --  -88.50 -78.00 -69.35   74
 68  \w   -107.00 -65.00   0.50    1.20    --  -88.50 -77.00 -24.32   84
 69  \w    -90.00 -63.00   0.50    1.20    --  -88.50 -80.00  41.10   54
 70  \w    -98.00 -67.00   0.50    1.20    --  -88.50 -71.00  13.46   62
 71  \w   -102.00 -67.00   0.50    1.20    --  -88.50 -70.00 151.27   70
 72  \w   -110.00 -73.00   0.50    1.20    --  -88.50 -66.00 176.85   74
 73  \w   -135.00 -65.00   0.50    1.20    --  -88.50 -79.00 103.21  140
 74  \w   -130.00-103.00   0.50    0.50    --  -60.00 -74.00  -6.73   54
 75  \w   -132.00-104.00   0.50    0.50    --  -60.00 -75.00 -74.91   56
 76  \w   -107.00 -68.00   0.50    1.20    --  -88.50 -77.00 -78.35   78
 77  \w   -116.00 -62.00   0.50    1.20    --  -88.50 -82.00-116.89  108
 78  \w   -119.00 -68.00   0.50    1.20    --  -88.50 -72.00-116.76  102
 79  \w   -146.00-102.00   0.50    1.20    --  -76.00 -82.00-158.26   88
 80  \w   -156.00-122.00   0.50    1.20    --  -84.00 -72.00-102.76   68
 81  \w   -148.00 -98.00   0.50    1.20    --  -88.50 -77.00-150.00  100
 82  \w   -152.00 -62.00   0.50    1.20    --  -88.50 -83.00-154.49  180
 83  \w   -143.00-116.00   0.50    1.20    --  -76.00 -74.00 -30.37   54
 84  \w   -157.00 -66.00   0.50    1.20    --  -88.50 -73.00   3.25  182
 85  \w   -137.00-106.00   0.50    1.20    --  -88.50 -81.00  83.63   62
 86  \w   -154.00 -89.00   0.50    1.20    --  -88.50-109.00 171.00  130
 87  \w   -157.00-103.00   0.50    1.20    --  -88.50 -73.00  45.57  108
 88  \w   -156.00-102.00   0.50    1.20    --  -88.50 -78.00 -69.35  108
 89  \w   -157.00 -62.00   0.50    1.20    --  -88.50 -83.00-124.19  190
 90  \w   -157.00-130.00   0.50    1.20    --  -88.50 -81.00  -0.37   54
 91  \w   -159.00-128.00   0.50    1.20    --  -88.50 -80.00  41.10   62
 92  \w   -158.00 -68.00   0.50    1.20    --  -88.50 -73.00  59.84  180
 93  \w   -153.00 -65.00   0.50    1.20    --  -88.50 -75.00 -53.30  176
 94  \w   -158.00-122.00   0.50    1.20    --  -88.50 -72.00-116.76   72
 95  \w   -160.00-108.00   0.50    1.20    --  -88.50 -81.00 -95.37  104
 96  \w   -159.00 -67.00   0.50    1.20    --  -88.50 -72.00 -40.04  184
 97  \w   -154.00-127.00   0.50    1.20    --  -88.50 -73.00 137.67   54
 98  \w   -155.00-115.00   0.50    1.20    --  -88.50 -66.00 176.85   80
 99  \w   -157.00-102.00   0.50    1.20    --  -88.50 -80.00 176.51  110
100  \w   -153.00-126.00   0.50    1.20    --  -88.50 -70.00 151.27   54
101  \w   -139.00-101.00   0.50    1.20    --  -88.50 -71.00  13.46   76
102  \w   -159.00-109.00   0.50    1.20    --  -88.50 -77.00 -78.35  100
103  \w    -82.00 -57.00   0.50    1.20    --  -88.50 109.00 -92.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0808
_diffrn_reflns_av_unetI/netI     0.0407
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_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            100729
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        64.491
_diffrn_reflns_theta_max         64.491
_diffrn_reflns_theta_min         2.479
_exptl_absorpt_coefficient_mu    5.848
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77452
_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            'metallic greenish green'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.414
_exptl_crystal_description       plate
_exptl_crystal_F_000             1584
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.086
_exptl_crystal_size_min          0.022
_refine_diff_density_max         1.845
_refine_diff_density_min         -1.724
_refine_diff_density_rms         0.133
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     856
_refine_ls_number_reflns         12300
_refine_ls_number_restraints     600
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0654
_refine_ls_R_factor_gt           0.0547
_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^)+(0.1086P)^2^+7.0813P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1540
_refine_ls_wR_factor_ref         0.1629
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10501
_reflns_number_total             12300
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc05455h3.cif
_cod_data_source_block           lzz-2019-0610-1
_cod_depositor_comments
'Adding full bibliography for 1568212--1568213.cif.'
_cod_original_cell_volume        3691.24(14)
_cod_database_code               1568212
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
2. Others
 Fixed Sof: Br1(0.5) Br2(0.5)
3.a Ternary CH refined with riding coordinates:
 C014(H014)
3.b Secondary CH2 refined with riding coordinates:
 C02O(H02A,H02I), C02P(H02O,H02P)
3.c Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00E(H00E), C00H(H00H), C00K(H00K), C00N(H00N), C00P(H00P),
 C00R(H00R), C00S(H00S), C00V(H00V), C00X(H00X), C00Z(H00Z), C010(H010),
 C011(H011), C012(H012), C013(H013), C015(H015), C016(H016), C017(H017),
 C018(H018), C01A(H01A), C01B(H01B), C01C(H01C), C01D(H01D), C01F(H01F),
 C01G(H01G), C01H(H01H), C01I(H01I), C01J(H01J), C01K(H01K), C01M(H01M),
 C01N(H01N), C01O(H01O), C01P(H01P), C01Q(H01Q), C01R(H01R), C01S(H01S),
 C01T(H01T), C01U(H01U), C01V(H01V), C01X(H01X), C01Y(H01Y), C01Z(H01Z),
 C020(H020), C021(H021), C022(H022), C023(H023), C024(H024), C025(H025),
 C026(H026), C027(H027), C028(H028), C029(H029), C02B(H02B), C02C(H02C),
 C02D(H02D), C02E(H02E), C02F(H02F), C02G(H02G), C02H(H02H), C02J(H02J),
 C02K(H02K), C02L(H02L), C02M(H02M), C02N(H02N)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              66745
_shelx_hkl_checksum              78807
_shelx_fab_checksum              55360
_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
;