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_4519158
_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         'C53 H72 B10 O0.69, 0.31(O), C6 H14'
_chemical_formula_sum            'C59 H86 B10 O'
_chemical_formula_weight         919.37
_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             2020-11-21
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                91.159(3)
_cell_angle_beta                 103.259(3)
_cell_angle_gamma                105.903(3)
_cell_formula_units_Z            2
_cell_length_a                   11.646(2)
_cell_length_b                   11.847(2)
_cell_length_c                   22.420(4)
_cell_measurement_reflns_used    2386
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      21.42
_cell_measurement_theta_min      2.29
_cell_volume                     2884.2(9)
_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 2014/5 (Sheldrick, 2014)'
_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 0.989
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_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  0.0784
_diffrn_reflns_av_unetI/netI     0.1387
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            26724
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.562
_diffrn_reflns_theta_min         1.875
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.058
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.4365
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1390 before and 0.0575 after correction.
The Ratio of minimum to maximum transmission is 0.5854.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.059
_exptl_crystal_description       block
_exptl_crystal_F_000             996
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.492
_refine_diff_density_min         -0.353
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     658
_refine_ls_number_reflns         13177
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.1550
_refine_ls_R_factor_gt           0.0775
_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^)+(0.0872P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1790
_refine_ls_wR_factor_ref         0.2200
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6644
_reflns_number_total             13177
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c04473_si_002.cif
_cod_data_source_block           23
_cod_database_code               4519158
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.994
_shelx_estimated_absorpt_t_min   0.990
_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. Uiso/Uaniso restraints and constraints
Uanis(C3) \\sim Ueq: with sigma of 0.0001 and sigma for terminal atoms of 0.0002
3. Others
 Sof(O1A)=1-FVAR(1)
 Sof(O1)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B)
4.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C8(H8), C9(H9), C15(H15), C16(H16), C18(H18), C19(H19),
 C25(H25), C26(H26), C28(H28), C29(H29), C35(H35), C36(H36), C38(H38), C39(H39),
  C45(H45), C46(H46), C48(H48), C49(H49), C3(H3)
4.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C31(H31A,H31B,H31C), C32(H32A,
 H32B,H32C), C33(H33A,H33B,H33C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C),
 C43(H43A,H43B,H43C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C53(H53A,H53B,
 H53C), C54(H54A,H54B,H54C), C59(H59A,H59B,H59C)
4.d Boron cage BH refined with riding coordinates:
 C2(H2), B7(H7), B8(H8A), B9(H9A), B10(H10), B12(H12)
;
_shelx_res_checksum              99549
_shelx_hkl_checksum              82379
_olex2_submission_special_instructions 'No special instructions were received'