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_4133011
_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         'C37 H42 B11 O2, C8 H20 N'
_chemical_formula_sum            'C45 H62 B11 N O2'
_chemical_formula_weight         767.86
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-06-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.7240(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.4673(2)
_cell_length_b                   16.6842(3)
_cell_length_c                   12.3236(2)
_cell_measurement_reflns_used    9389
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      54.97
_cell_measurement_theta_min      4.264
_cell_volume                     2205.23(7)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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      170.01
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0566
_diffrn_reflns_av_unetI/netI     0.0456
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            32003
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         54.945
_diffrn_reflns_theta_min         3.336
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.312
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.5693
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1378 before and 0.0846 after correction. The Ratio of minimum to maximum transmission is 0.7552. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.156
_exptl_crystal_description       plate
_exptl_crystal_F_000             820
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.404
_refine_diff_density_min         -0.286
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 3813 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     545
_refine_ls_number_reflns         8373
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0433
_refine_ls_R_factor_gt           0.0425
_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^)+(0.0775P)^2^+0.1601P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1108
_refine_ls_wR_factor_ref         0.1119
_reflns_Friedel_coverage         0.927
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                8196
_reflns_number_total             8373
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b07872_si_002.cif
_cod_data_source_block           wmj18105_0m
_cod_database_code               4133011
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.997
_shelx_estimated_absorpt_t_min   0.964
_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.a Secondary CH2 refined with riding coordinates:
 C38(H38A,H38B), C40(H40A,H40B), C42(H42A,H42B), C44(H44A,H44B)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C7(H7), C8(H8), C11(H11), C12(H12), C14(H14), C15(H15),
 C18(H18), C19(H19), C21(H21), C22(H22), C25(H25), C26(H26), C28(H28), C29(H29),
  C32(H32), C33(H33), C35(H35), C36(H36)
2.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C16(H16A,H16B,H16C), C23(H23A,H23B,H23C), C30(H30A,H30B,
 H30C), C37(H37A,H37B,H37C), C39(H39A,H39B,H39C), C41(H41A,H41B,H41C), C43(H43A,
 H43B,H43C), C45(H45A,H45B,H45C)
2.d Boron cage BH refined with riding coordinates:
 B7(H7A), B8(H8A), B9(H9), B10(H10), B11(H11A), B12(H12A)
;
_shelx_res_checksum              36428
_shelx_hkl_checksum              99604
_olex2_submission_special_instructions 'No special instructions were received'