Variable Metal Chelation Modes and Activation Sequence in Pd-Catalyzed B–H Poly-arylation of Carboranes
Cao, Hou-ji; Chen, Meng; Sun, Fangxiang; Zhao, Yue; Lu, Changsheng; Zhang, Xiaolei; Shi, Zhuangzhi; Yan, Hong; ACS Catalysis 11 (2021) 14047–14057; doi:10.1021/acscatal.1c04473

data_4519156
_publ_section_title
;
 Variable Metal Chelation Modes and Activation Sequence in Pd-Catalyzed
 B--H Poly-arylation of Carboranes
;
_journal_issue                   22
_journal_name_full               'ACS Catalysis'
_journal_page_first              14047
_journal_page_last               14057
_journal_paper_doi               10.1021/acscatal.1c04473
_journal_volume                  11
_journal_year                    2021
_chemical_formula_moiety         'C45 H55 B10 N O2'
_chemical_formula_sum            'C45 H55 B10 N O2'
_chemical_formula_weight         749.99
_space_group_crystal_system      orthorhombic
_space_group_IT_number           16
_space_group_name_Hall           'P 2 2'
_space_group_name_H-M_alt        'P 2 2 2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-11-13
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.541(3)
_cell_length_b                   21.748(3)
_cell_length_c                   21.850(3)
_cell_measurement_reflns_used    4698
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      23.765
_cell_measurement_theta_min      2.315
_cell_volume                     9761(2)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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      296.15
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.835
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  apex
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1395
_diffrn_reflns_av_unetI/netI     0.1218
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.835
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            91128
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.833
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.436
_diffrn_reflns_theta_min         1.652
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.058
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5978
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1754 before and 0.0954 after correction. The Ratio of minimum to maximum transmission is 0.8018. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.021
_exptl_crystal_description       block
_exptl_crystal_F_000             3184
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.244
_refine_diff_density_min         -0.286
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   -2(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.957
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1071
_refine_ls_number_reflns         22548
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      0.957
_refine_ls_R_factor_all          0.1428
_refine_ls_R_factor_gt           0.0683
_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^)+(0.0850P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1512
_refine_ls_wR_factor_ref         0.1897
_reflns_Friedel_coverage         0.852
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.829
_reflns_number_gt                12058
_reflns_number_total             22548
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c04473_si_002.cif
_cod_data_source_block           15d
_cod_depositor_comments
;

2025-07-30
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C90 H110 B20 N2 O4'
_cod_original_formula_weight         1499.99
_cod_original_formula_moiety         '2(C45 H55 B10 N O2)'
_cod_original_formula_units_Z            4
_cod_database_code               4519156
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.994
_shelx_estimated_absorpt_t_min   0.991
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 3(2)
 -2(2)
2. 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, All O(H) groups
3. Restrained distances
 H1A-O1A
 0.82 with sigma of 0.001
 H1A-O2A
 2.781 with sigma of 0.001
4.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C4A(H4AA,H4AB)
4.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C9(H9), C11(H11), C15(H15), C17(H17), C19(H19), C23(H23),
 C25(H25), C27(H27), C31(H31), C33(H33), C35(H35), C39(H39), C41(H41), C43(H43),
  C3A(H3A), C7A(H7AA), C9A(H9AA), C11A(H11B), C15A(H15A), C17A(H17A),
 C19A(H19A), C23A(H23A), C25A(H25A), C27A(H27A), C31A(H31A), C33A(H33A),
 C35A(H35A), C39A(H39A), C41A(H41A), C43A(H43A)
4.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C36(H36A,H36B,H36C), C37(H37A,
 H37B,H37C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C12A(H12D,H12E,H12F),
 C13A(H13D,H13E,H13F), C20A(H20D,H20E,H20F), C21A(H21D,H21E,H21F), C28A(H28D,
 H28E,H28F), C29A(H29D,H29E,H29F), C36A(H36D,H36E,H36F), C37A(H37D,H37E,H37F),
 C44A(H44D,H44E,H44F), C45A(H45D,H45E,H45F)
4.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
4.e Boron cage BH refined with riding coordinates:
 C2(H2), B7(H7A), B8(H8), B9(H9A), B10(H10), B11(H11A), C2A(H2A), B7A(H7AB),
 B8A(H8A), B9A(H9AB), B10A(H10A), B11A(H11C)
;
_shelx_res_checksum              28906
_shelx_hkl_checksum              40101
_shelx_fab_checksum              57433
_olex2_submission_special_instructions 'No special instructions were received'