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_1568213
_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         'C96 H73 Br N Os P3, C2 H4 Cl2, Br'
_chemical_formula_sum            'C98 H77 Br2 Cl2 N Os P3'
_chemical_formula_weight         1782.43
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_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                90
_cell_angle_beta                 106.0800(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   37.0917(4)
_cell_length_b                   10.98180(10)
_cell_length_c                   43.2112(5)
_cell_measurement_reflns_used    47463
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      67.5380
_cell_measurement_theta_min      3.6720
_cell_volume                     16912.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.980
_diffrn_measured_fraction_theta_max 0.980
_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    -25.00  37.00   0.50    0.30    --  -43.22  19.00  30.00  124
  2  \w    -42.00  20.00   0.50    0.30    --  -43.22  38.00-180.00  124
  3  \w    104.00 133.00   0.50    0.70    --   93.75 103.00-143.00   58
  4  \w     95.00 124.00   0.50    0.70    --   93.75 125.00  90.00   58
  5  \w    140.00 166.00   0.50    0.70    --   93.75 125.00  90.00   52
  6  \w    -26.00  37.00   0.50    0.30    --  -43.22  19.00 -90.00  126
  7  \w    -26.00  12.00   0.50    0.30    --  -43.22  19.00 150.00   76
  8  \w    -46.00 -15.00   0.50    0.70    --  -90.25  77.00 120.00   62
  9  \w   -101.00 -53.00   0.50    0.70    --  -90.25  77.00 120.00   96
 10  \w    -39.00 -13.00   0.50    0.70    --  -90.25  45.00 120.00   52
 11  \w    -49.00 -17.00   0.50    0.70    --  -90.25  45.00  60.00   64
 12  \w    -50.00 -13.00   0.50    0.70    --  -90.25  45.00  30.00   74
 13  \w    -42.00 -15.00   0.50    0.70    --  -90.25  45.00   0.00   54
 14  \w    -85.00 -50.00   0.50    0.70    --  -90.25 125.00   0.00   70
 15  \w    -91.00 -56.00   0.50    0.70    --  -90.25 125.00-120.00   70
 16  \w    -40.00 -15.00   0.50    0.70    --  -90.25 125.00-120.00   50
 17  \w    -85.00 -29.00   0.50    0.70    --  -90.25 103.00-143.00  112
 18  \w    -82.00 -18.00   0.50    0.70    --  -90.25 125.00 150.00  128
 19  \w    -52.00 -17.00   0.50    0.30    --  -43.22 125.00 120.00   70
 20  \w    -90.00 -64.00   0.50    0.30    --  -43.22 125.00 120.00   52
 21  \w    -70.00   3.00   0.50    0.30    --  -43.22 103.00-143.00  146
 22  \w   -129.00 -81.00   0.50    0.70    --  -90.25-103.00 114.00   96
 23  \w   -150.00 -88.00   0.50    0.70    --  -90.25 -94.00  90.00  124
 24  \w   -165.00 -97.00   0.50    0.70    --  -90.25 -30.00 150.00  136
 25  \w    -93.00 -64.00   0.50    0.70    --  -90.25 -30.00 150.00   58
 26  \w   -112.00 -86.00   0.50    0.70    --  -90.25-125.00  60.00   52
 27  \w   -145.00-117.00   0.50    0.70    --  -90.25-125.00  60.00   56
 28  \w   -110.00 -82.00   0.50    0.30    --  -43.22-125.00 -90.00   56
 29  \w     37.00 117.00   0.50    0.70    --   93.75-125.00 150.00  160
 30  \w     57.00 111.00   0.50    0.70    --   93.75-103.00 114.00  108
 31  \w     45.00 115.00   0.50    0.70    --   93.75-125.00  30.00  140
 32  \w     55.00  96.00   0.50    0.70    --   93.75 -94.00-120.00   82
 33  \w     20.00  46.00   0.50    0.30    --   43.22-103.00 114.00   52
 34  \w     20.00  46.00   0.50    0.70    --   93.75 -61.00 150.00   52
 35  \w     43.00  68.00   0.50    0.70    --   93.75 -61.00 120.00   50
 36  \w     17.00  42.00   0.50    0.70    --   93.75 -45.00 120.00   50
 37  \w     25.00  71.00   0.50    0.70    --   93.75 -61.00   0.00   92
 38  \w     27.00  71.00   0.50    0.70    --   93.75 -61.00 -90.00   88
 39  \w     22.00  67.00   0.50    0.70    --   93.75 -61.00-120.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0219962000
_diffrn_orient_matrix_UB_12      0.0375064000
_diffrn_orient_matrix_UB_13      0.0344043000
_diffrn_orient_matrix_UB_21      -0.0080044000
_diffrn_orient_matrix_UB_22      0.1350138000
_diffrn_orient_matrix_UB_23      -0.0090151000
_diffrn_orient_matrix_UB_31      -0.0363420000
_diffrn_orient_matrix_UB_32      -0.0070325000
_diffrn_orient_matrix_UB_33      0.0105677000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0321
_diffrn_reflns_av_unetI/netI     0.0208
_diffrn_reflns_Laue_measured_fraction_full 0.980
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -44
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       51
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_number            81743
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.538
_diffrn_reflns_theta_max         67.538
_diffrn_reflns_theta_min         2.785
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.428
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70718
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.80a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear greenish green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.400
_exptl_crystal_description       block
_exptl_crystal_F_000             7176
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.681
_refine_diff_density_min         -1.669
_refine_diff_density_rms         0.120
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1168
_refine_ls_number_reflns         14941
_refine_ls_number_restraints     132
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0520
_refine_ls_R_factor_gt           0.0495
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0560P)^2^+211.1026P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1288
_refine_ls_wR_factor_ref         0.1305
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14112
_reflns_number_total             14941
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc05455h3.cif
_cod_data_source_block           lzz-200709-1
_cod_depositor_comments
'Adding full bibliography for 1568212--1568213.cif.'
_cod_database_code               1568213
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C648 H584 Br8 N96 Os8 P24 '
_shelx_estimated_absorpt_t_max   0.613
_shelx_estimated_absorpt_t_min   0.410
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     62.30
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
C33 \\sim C32 \\sim C46 \\sim C45 \\sim C44 \\sim C34: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01 within 2A
C02R \\sim C02V \\sim C02T \\sim C02P \\sim C03A \\sim C02M: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C38 \\sim C35 \\sim C30 \\sim C31 \\sim C43: within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01 within 2A
Uanis(C02P) \\sim Ueq, Uanis(C03A) \\sim Ueq, Uanis(C02M) \\sim Ueq,
Uanis(C02R) \\sim Ueq, Uanis(C02V) \\sim Ueq, Uanis(C02T) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
2. Others
 Fixed Sof: C02M(0.5) H02M(0.5) C02P(0.5) H02P(0.5) C02R(0.5) H02R(0.5)
 C02T(0.5) C02V(0.5) C03A(0.5) C30(0.5) C35(0.5) H35(0.5) C38(0.5) H38(0.5)
 C43(0.5) H43(0.5) C31(0.5) H31(0.5) C36(0.5) C42(0.5) H42(0.5) C41(0.5)
 H41(0.5) C40(0.5) H40(0.5) C39(0.5) H39(0.5) C37(0.5) H37(0.5) C32(0.5)
 H32(0.5) C44(0.5) H44(0.5) C34(0.5) H34(0.5) C33(0.5) C45(0.5) H45(0.5)
 C46(0.5) H46(0.5) C47(0.5) C50(0.5) H50(0.5) C49(0.5) H49(0.5) C48(0.5)
 H48(0.5) C51B(0.5) H51B(0.5) C52(0.5) H52(0.5) C53(0.5) H53(0.5) C59(0.5)
 H59(0.5) C56(0.5) H56(0.5) C57(0.5) H57(0.5) C58(0.5) H58(0.5) C54(0.5)
 H1B(0.5) H1A(0.5) C61(0.5) H61(0.5) C85(0.5) C62(0.5) H62(0.5) C65(0.5)
 H65(0.5) C63(0.5) H63(0.5) C67(0.5) H67(0.5) C64(0.5) H60B(0.5) H60A(0.5)
 C66(0.5) H66(0.5) C55(0.5) H55(0.5) C68(0.5) H68(0.5) C51A(0.5) H51A(0.5)
 Br1(0.5) Br2(0.5)
3.a Ternary CH refined with riding coordinates:
 C51B(H51B), C51A(H51A)
3.b Secondary CH2 refined with riding coordinates:
 C02H(H02A,H02B), C02J(H02C,H02D)
3.c Aromatic/amide H refined with riding coordinates:
 C00C(H00C), C00G(H00G), C00K(H00K), C00L(H00L), C00M(H00M), C00N(H00N),
 C00O(H00O), C00S(H00S), C00W(H00W), C00Z(H00Z), C010(H010), C011(H011),
 C012(H012), C4(H4), C24(H24), C5(H5), C019(H019), C01A(H01A), C01B(H01B),
 C25(H25), C6(H6), C22(H22), C01F(H01F), C01G(H01G), C7(H7), C01I(H01I), C8(H8),
  C01K(H01K), C15(H15), C01M(H01M), C23(H23), C9(H9), C01P(H01P), C01R(H01R),
 C17(H17), C18(H18), C10(H10), C01V(H01V), C26(H26), C27(H27), C11(H11),
 C01Z(H01Z), C19(H19), C12(H12), C20(H20), C023(H023), C024(H024), C13(H13),
 C28(H28), C14(H14), C029(H029), C29(H29), C02M(H02M), C02P(H02P), C02R(H02R),
 C35(H35), C38(H38), C43(H43), C31(H31), C42(H42), C41(H41), C40(H40), C39(H39),
  C37(H37), C32(H32), C44(H44), C34(H34), C45(H45), C46(H46), C50(H50),
 C49(H49), C48(H48), C52(H52), C53(H53), C59(H59), C56(H56), C57(H57), C58(H58),
  C1(H1B), C1(H1A), C61(H61), C62(H62), C65(H65), C63(H63), C67(H67),
 C60B(H60B), C60B(H60A), C66(H66), C55(H55), C60(H60), C68(H68)
3.d Fitted hexagon refined as free rotating group:
 C36(C42,C41,C40,C39,C37)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              75967
_shelx_hkl_checksum              83184
_shelx_fab_checksum              56492
_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 1.629
_oxdiff_exptl_absorpt_empirical_full_min 0.661