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_4519157
_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         'C54 H73 B10 N'
_chemical_formula_sum            'C54 H73 B10 N'
_chemical_formula_weight         844.23
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-02-06
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_cell_angle_alpha                90
_cell_angle_beta                 103.168(19)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.427(12)
_cell_length_b                   37.88(4)
_cell_length_c                   13.129(13)
_cell_measurement_reflns_used    3872
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      21.353
_cell_measurement_theta_min      2.599
_cell_volume                     6018(10)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  apex
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1445
_diffrn_reflns_av_unetI/netI     0.1478
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       45
_diffrn_reflns_limit_k_min       -45
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            44669
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         1.681
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    0.050
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    0.932
_exptl_crystal_description       needle
_exptl_crystal_F_000             1816
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.33
_refine_diff_density_max         0.686
_refine_diff_density_min         -0.416
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     638
_refine_ls_number_reflns         10558
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.1470
_refine_ls_R_factor_gt           0.0940
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1721P)^2^+0.1656P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2610
_refine_ls_wR_factor_ref         0.3200
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5890
_reflns_number_total             10558
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c04473_si_002.cif
_cod_data_source_block           16
_cod_database_code               4519157
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.984
_shelx_estimated_absorpt_t_min   0.980
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-H3
 1.72 with sigma of 0.005
 C3-H3
 0.93 with sigma of 0.005
3. Others
 Sof(C51A)=Sof(H51D)=Sof(H51E)=Sof(H51F)=1-FVAR(1)
 Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=FVAR(1)
 Sof(C52A)=Sof(H52D)=Sof(H52E)=Sof(H52F)=1-FVAR(2)
 Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=FVAR(2)
 Sof(C53A)=Sof(H53D)=Sof(H53E)=Sof(H53F)=1-FVAR(3)
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=FVAR(3)
4.a Riding coordinates:
 C2(H2), C43(H43), B7(H7A), B8(H8), B9(H9A), B10(H10A), B12(H12)
4.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C9(H9), C10(H10), C16(H16), C17(H17), C19(H19), C20(H20),
 C26(H26), C27(H27), C29(H29), C30(H30), C36(H36), C37(H37), C39(H39), C40(H40),
  C46(H46), C47(H47), C49(H49), C50(H50)
4.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,
 H14C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C32(H32A,
 H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C42(H42A,H42B,H42C),
 C44(H44A,H44B,H44C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C53(H53A,H53B,
 H53C), C51A(H51D,H51E,H51F), C52A(H52D,H52E,H52F), C53A(H53D,H53E,H53F)
;
_shelx_res_checksum              57821
_shelx_hkl_checksum              48207
_shelx_fab_checksum              19366
_olex2_submission_special_instructions 'No special instructions were received'