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_4133008
_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_formula_moiety
'C37 H42 B11 O2, 1.7(C4 H8 O), C8 H20 N, 0.3(C H3 O)'
_chemical_formula_sum            'C52.09 H76.48 B11 N O4'
_chemical_formula_weight         899.58
_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
_audit_creation_date             2018-06-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 106.874(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.1297(9)
_cell_length_b                   12.7407(6)
_cell_length_c                   23.8742(13)
_cell_measurement_reflns_used    4837
_cell_measurement_temperature    120.2
_cell_measurement_theta_max      29.3504
_cell_measurement_theta_min      2.8803
_cell_volume                     5277.2(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      120.2
_diffrn_detector_area_resol_mean 10.3592
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_details
;
  1 omega  -81.00    8.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.4683  -38.0000  -90.0000 89

  2 omega  -22.00   65.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.4683   77.0000   30.0000 87

  3 omega  -45.00  -19.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -       11.7808  138.0000   77.0000 26
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0197824000
_diffrn_orient_matrix_UB_12      0.0038709000
_diffrn_orient_matrix_UB_13      -0.0215418000
_diffrn_orient_matrix_UB_21      -0.0356858000
_diffrn_orient_matrix_UB_22      -0.0019362000
_diffrn_orient_matrix_UB_23      -0.0223423000
_diffrn_orient_matrix_UB_31      -0.0026446000
_diffrn_orient_matrix_UB_32      0.0555134000
_diffrn_orient_matrix_UB_33      0.0007240000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0402
_diffrn_reflns_av_unetI/netI     0.0544
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            23314
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.348
_diffrn_reflns_theta_min         3.320
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.066
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94877
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.132
_exptl_crystal_description       block
_exptl_crystal_F_000             1932
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.32
_refine_diff_density_max         0.599
_refine_diff_density_min         -0.385
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     666
_refine_ls_number_reflns         9570
_refine_ls_number_restraints     46
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.1069
_refine_ls_R_factor_gt           0.0735
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1069P)^2^+2.6785P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1872
_refine_ls_wR_factor_ref         0.2167
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6529
_reflns_number_total             9570
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b07872_si_003.cif
_cod_data_source_block           170601_lfr_0407
_cod_database_code               4133008
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C10 H10 N2 O8 b1'
_shelx_estimated_absorpt_t_max   0.979
_shelx_estimated_absorpt_t_min   0.973
_reflns_odcompleteness_completeness 99.63
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Restrained distances
 C51-C50
 1.53 with sigma of 0.02
 O1-H1
 0.85 with sigma of 0.02
 C49-C50 = C52-C51
 1.53 with sigma of 0.02
 O49B-C52B = O49B-C49B
 1.43 with sigma of 0.02
 C52B-C51B = C51B-C50B = C50B-C49B
 1.53 with sigma of 0.02
 C52-C50
 2.5 with sigma of 0.04
 C51-C49
 2.5 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O4 \\sim C49 \\sim C50 \\sim C51 \\sim C52: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C51B \\sim C50B \\sim C52B \\sim O49B \\sim C49B: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08
C52B \\sim C51B \\sim C50B \\sim C49B \\sim O49B: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08
4. Others
 Sof(C52B)=Sof(H52C)=Sof(H52D)=Sof(O49B)=Sof(C49B)=Sof(H49C)=Sof(H49D)=
 Sof(C50B)=Sof(H50C)=Sof(H50D)=Sof(C51B)=Sof(H51C)=Sof(H51D)=1-FVAR(1)
 Sof(O4)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(C51)=
 Sof(H51A)=Sof(H51B)=Sof(C52)=Sof(H52A)=Sof(H52B)=FVAR(1)
 Sof(O5B)=Sof(C60B)=Sof(H60A)=Sof(H60B)=Sof(H60C)=1-FVAR(2)
 Sof(O3)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(C47)=
 Sof(H47A)=Sof(H47B)=Sof(C48)=Sof(H48A)=Sof(H48B)=FVAR(2)
5.a Riding coordinates:
 C51B(H51C,H51D)
5.b Secondary CH2 refined with riding coordinates:
 C45(H45A,H45B), C46(H46A,H46B), C47(H47A,H47B), C48(H48A,H48B), C49(H49A,
 H49B), C50(H50A,H50B), C51(H51A,H51B), C52(H52A,H52B), C37(H37A,H37B),
 C39(H39A,H39B), C41(H41A,H41B), C43(H43A,H43B), C52B(H52C,H52D), C49B(H49C,
 H49D), C50B(H50C,H50D)
5.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C7(H7), C8(H8), C11(H11), C13(H13), C14(H14), C15(H15),
 C17(H17), C19(H19), C20(H20), C21(H21), C24(H24), C26(H26), C27(H27), C28(H28),
  C31(H31), C33(H33), C34(H34), C35(H35)
5.d Idealised Me refined as rotating group:
 C0AA(H0AA,H0AB,H0AC), C9(H9A,H9B,H9C), C22(H22A,H22B,H22C), C29(H29A,H29B,
 H29C), C36(H36A,H36B,H36C), C38(H38A,H38B,H38C), C40(H40A,H40B,H40C), C42(H42A,
 H42B,H42C), C44(H44A,H44B,H44C), C60B(H60A,H60B,H60C)
5.e Boron cage BH refined with riding coordinates:
 B6(H6A), B7(H7A), B8(H8A), B9(H9), B10(H10), B11(H11A)
;
_shelx_res_checksum              62882
_shelx_hkl_checksum              22787
_olex2_submission_special_instructions 'No special instructions were received'