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_4519160
_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         'C93 H67 B10 N5 O6'
_chemical_formula_sum            'C93 H67 B10 N5 O6'
_chemical_formula_weight         1458.61
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2021-08-28
_audit_creation_method
;
Olex2 1.5
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6392)
;
_cell_angle_alpha                100.657(10)
_cell_angle_beta                 92.975(11)
_cell_angle_gamma                92.071(11)
_cell_formula_units_Z            2
_cell_length_a                   10.8160(18)
_cell_length_b                   16.257(3)
_cell_length_c                   21.721(4)
_cell_measurement_reflns_used    6032
_cell_measurement_temperature    193.00
_cell_measurement_theta_max      59.190
_cell_measurement_theta_min      2.409
_cell_volume                     3744.3(12)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      193.00
_diffrn_measured_fraction_theta_full 0.963
_diffrn_measured_fraction_theta_max 0.963
_diffrn_measurement_device_type  'Bruker D8 VENTURE Metaljet PHOTON II'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.1321
_diffrn_reflns_av_unetI/netI     0.2083
_diffrn_reflns_Laue_measured_fraction_full 0.963
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            41699
_diffrn_reflns_point_group_measured_fraction_full 0.963
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        51.249
_diffrn_reflns_theta_max         51.249
_diffrn_reflns_theta_min         1.804
_diffrn_source_current           2.86
_diffrn_source_power             0.19937059999999998
_diffrn_source_voltage           69.71
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.391
_exptl_absorpt_correction_T_max  0.7518
_exptl_absorpt_correction_T_min  0.6385
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1235 before and 0.0737 after correction.
The Ratio of minimum to maximum transmission is 0.8493.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.294
_exptl_crystal_description       block
_exptl_crystal_F_000             1516
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.247
_refine_diff_density_min         -0.230
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1271
_refine_ls_number_reflns         11880
_refine_ls_number_restraints     1684
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.2533
_refine_ls_R_factor_gt           0.1008
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0520P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2114
_refine_ls_wR_factor_ref         0.2683
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3814
_reflns_number_total             11880
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c04473_si_002.cif
_cod_data_source_block           18
_cod_database_code               4519160
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.962
_shelx_estimated_absorpt_t_min   0.955
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups
2. Restrained distances
 N7-C101 \\sim N5-C67
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C93 \\sim C97 \\sim C98 \\sim C96 \\sim C95 \\sim C94: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C90 \\sim C92 \\sim C99 \\sim C91 \\sim C88 \\sim C89: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C110 \\sim C109 \\sim C111 \\sim C119 \\sim C118 \\sim C120 \\sim N7 \\sim C113
\\sim C112 \\sim O9 \\sim C117 \\sim C116 \\sim C115 \\sim C114 \\sim C101:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O7 \\sim O8 \\sim C5: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
Uanis(C90) \\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C99) \\sim Ueq, Uanis(C89)
\\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(O5) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O6) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Sof(H52)=Sof(C100)=Sof(H100)=Sof(C101)=Sof(C102)=Sof(H102)=1-FVAR(1)
 Sof(H52A)=Sof(C67)=Sof(C75)=Sof(H75)=Sof(C82)=Sof(H82)=FVAR(1)
 Sof(O6)=Sof(C93)=Sof(C94)=Sof(C95)=Sof(H95)=Sof(C96)=Sof(H96)=Sof(C97)=
 Sof(H97)=Sof(C98)=Sof(H98)=Sof(C103)=Sof(C104)=Sof(H104)=Sof(C105)=Sof(H105)=
 Sof(C106)=Sof(H106)=Sof(C107)=Sof(H107)=Sof(C108)=Sof(N6)=1-FVAR(2)
 Sof(N4)=Sof(C38)=Sof(C39)=Sof(C40)=Sof(H40)=Sof(C41)=Sof(H41)=Sof(C42)=
 Sof(H42)=Sof(C43)=Sof(H43)=Sof(O5)=Sof(C88)=Sof(C89)=Sof(C90)=Sof(H90)=
 Sof(C91)=Sof(H91)=Sof(C92)=Sof(H92)=Sof(C99)=Sof(H99)=FVAR(2)
 Sof(H5B)=Sof(O8)=1-FVAR(3)
 Sof(H5A)=Sof(O7)=FVAR(3)
 Sof(O9)=Sof(N7)=Sof(C109)=Sof(C110)=Sof(C111)=Sof(H111)=Sof(C112)=Sof(C113)=
 Sof(C114)=Sof(H114)=Sof(C115)=Sof(H115)=Sof(C116)=Sof(H116)=Sof(C117)=
 Sof(H117)=Sof(C118)=Sof(H118)=Sof(C119)=Sof(H119)=Sof(C120)=Sof(H120)=1-FVAR(4)
 Sof(O4)=Sof(N5)=Sof(C48)=Sof(C49)=Sof(C55)=Sof(H55)=Sof(C59)=Sof(H59)=
 Sof(C61)=Sof(C70)=Sof(C78)=Sof(H78)=Sof(C81)=Sof(H81)=Sof(C83)=Sof(H83)=
 Sof(C85)=Sof(H85)=Sof(C86)=Sof(H86)=Sof(C87)=Sof(H87)=FVAR(4)
6.a Aromatic/amide H refined with riding coordinates:
 C5(H5A), C5(H5B), C7(H7), C10(H10), C13(H13), C14(H14), C15(H15), C17(H17),
 C19(H19), C22(H22), C24(H24), C25(H25), C27(H27), C31(H31), C34(H34), C35(H35),
  C36(H36), C40(H40), C41(H41), C42(H42), C43(H43), C44(H44), C46(H46),
 C50(H50), C51(H51), C52(H52A), C52(H52), C53(H53), C54(H54), C55(H55),
 C56(H56), C57(H57), C58(H58), C59(H59), C60(H60), C62(H62), C63(H63), C64(H64),
  C65(H65), C66(H66), C68(H68), C69(H69), C71(H71), C72(H72), C73(H73),
 C74(H74), C75(H75), C76(H76), C77(H77), C78(H78), C79(H79), C80(H80), C81(H81),
  C82(H82), C83(H83), C84(H84), C85(H85), C86(H86), C87(H87), C90(H90),
 C91(H91), C92(H92), C95(H95), C96(H96), C97(H97), C98(H98), C99(H99),
 C100(H100), C102(H102), C104(H104), C105(H105), C106(H106), C107(H107),
 C111(H111), C114(H114), C115(H115), C116(H116), C117(H117), C118(H118),
 C119(H119), C120(H120)
6.b Fitted hexagon refined as free rotating group:
 C38(C39,C40,C41,C42,C43), C93(C94,C95,C96,C97,C98), C103(C104,C105,C106,C107,
 C108), C112(C113,C114,C115,C116,C117)
6.c Boron cage BH refined with riding coordinates:
 C23(H23), B2(H2), B6(H6), B8(H8), B9(H9), B10(H10A)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              26484
_shelx_hkl_checksum              67220
_shelx_fab_checksum              70486
_olex2_submission_special_instructions 'No special instructions were received'