Palladium-Catalyzed Selective Five-Fold Cascade Arylation of the 12-Vertex Monocarborane Anion by B-H Activation.
Lin, Furong; Yu, Jing-Lu; Shen, Yunjun; Zhang, Shuo-Qing; Spingler, Bernhard; Liu, Jiyong; Hong, Xin; Duttwyler, Simon; Journal of the American Chemical Society 140 (2018) 13798–13807; doi:10.1021/jacs.8b07872

data_4133009
_publ_section_title
;
 Palladium-Catalyzed Selective Five-Fold Cascade Arylation of the
 12-Vertex Monocarborane Anion by B-H Activation.
;
_journal_issue                   42
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13798
_journal_page_last               13807
_journal_paper_doi               10.1021/jacs.8b07872
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration rmad
_chemical_formula_moiety         '2(C31 H22 B11 Cl10), 2(C8 H20 N), C H2 Cl2'
_chemical_formula_sum            'C79 H86 B22 Cl22 N2'
_chemical_formula_weight         2081.21
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-09-28
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.6290(5)
_cell_length_b                   14.9866(5)
_cell_length_c                   22.4078(7)
_cell_measurement_reflns_used    9591
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      29.2910
_cell_measurement_theta_min      2.8605
_cell_volume                     4912.7(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      150.0
_diffrn_detector_area_resol_mean 10.3592
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_details
;
  1 omega  -32.00   19.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       11.7808  106.0000  134.0000 51

  2 omega  -64.00   38.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       11.7808  -38.0000  150.0000 102

  3 omega  -64.00   38.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       11.7808  -38.0000 -120.0000 102

  4 omega    3.00   54.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       11.7808 -106.0000   45.0000 51
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0478526000
_diffrn_orient_matrix_UB_12      -0.0061807000
_diffrn_orient_matrix_UB_13      -0.0029735000
_diffrn_orient_matrix_UB_21      0.0027565000
_diffrn_orient_matrix_UB_22      0.0124271000
_diffrn_orient_matrix_UB_23      -0.0304872000
_diffrn_orient_matrix_UB_31      0.0072991000
_diffrn_orient_matrix_UB_32      -0.0452521000
_diffrn_orient_matrix_UB_33      -0.0079731000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0445
_diffrn_reflns_av_unetI/netI     0.0422
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            33238
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.347
_diffrn_reflns_theta_min         3.054
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.654
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89628
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.407
_exptl_crystal_description       block
_exptl_crystal_F_000             2116
_exptl_crystal_size_max          0.49
_exptl_crystal_size_mid          0.46
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.832
_refine_diff_density_min         -0.584
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Flack x determined using 3038 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.03(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     611
_refine_ls_number_reflns         8913
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0712
_refine_ls_R_factor_gt           0.0609
_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^)+(0.0994P)^2^+4.3400P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1600
_refine_ls_wR_factor_ref         0.1712
_reflns_Friedel_coverage         0.810
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                7831
_reflns_number_total             8913
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b07872_si_006.cif
_cod_data_source_block           170928_lfr_0421
_cod_original_cell_volume        4912.6(3)
_cod_database_code               4133009
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'c h n o b cl'
_shelx_estimated_absorpt_t_max   0.838
_shelx_estimated_absorpt_t_min   0.740
_reflns_odcompleteness_completeness 99.68
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(Cl3A)=1-FVAR(1)
 Sof(Cl3)=FVAR(1)
 Sof(Cl6A)=1-FVAR(2)
 Sof(Cl6)=FVAR(2)
 Sof(Cl)=1-FVAR(3)
 Sof(Cl10)=FVAR(3)
 Fixed Sof: Cl11(0.5) Cl12(0.5) C40(0.5) H40A(0.5) H40B(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C36(H36A,H36B), C38(H38A,H38B), C34(H34A,H34B), C32(H32A,H32B), C40(H40A,H40B)
3.b Aromatic/amide H refined with riding coordinates:
 C27(H27), C23(H23), C21(H21), C7(H7), C25(H25), C3(H3), C5(H5), C15(H15),
 C31(H31), C13(H13), C17(H17), C19(H19), C29(H29), C9(H9A), C11(H11A)
3.c Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C), C39(H39A,H39B,H39C), C33(H33A,H33B,H33C), C35(H35A,H35B,
 H35C)
3.d Boron cage BH refined with riding coordinates:
 C1(H1), B10(H10), B6(H6), B11(H11), B8(H8), B7(H7A), B9(H9)
;
_shelx_res_checksum              15187
_shelx_hkl_checksum              98975
_olex2_submission_special_instructions 'No special instructions were received'