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_4133010
_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         '2(C3 H6 O), C8 H20 N, C31 H27 B11 Br5'
_chemical_formula_sum            'C45 H59 B11 Br5 N O2'
_chemical_formula_weight         1164.39
_space_group_crystal_system      orthorhombic
_space_group_IT_number           57
_space_group_name_Hall           '-P 2c 2b'
_space_group_name_H-M_alt        'P b c m'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-06-21
_audit_creation_method
;
Olex2 1.2
(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            4
_cell_length_a                   7.2360(3)
_cell_length_b                   26.5714(13)
_cell_length_c                   26.8768(9)
_cell_measurement_reflns_used    6843
_cell_measurement_temperature    137.1
_cell_measurement_theta_max      29.3397
_cell_measurement_theta_min      2.8093
_cell_volume                     5167.6(4)
_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)'
_diffrn_ambient_temperature      137.1
_diffrn_detector_area_resol_mean 10.3592
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -53.00   38.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       11.7808  -38.0000   60.0000 91

  2 omega  -19.00   84.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       11.7808   77.0000  -30.0000 103

  3 omega  -15.00   87.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       11.7808   38.0000 -120.0000 102
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0253518000
_diffrn_orient_matrix_UB_12      -0.0081152000
_diffrn_orient_matrix_UB_13      0.0055368000
_diffrn_orient_matrix_UB_21      -0.0082608000
_diffrn_orient_matrix_UB_22      0.0250865000
_diffrn_orient_matrix_UB_23      -0.0028416000
_diffrn_orient_matrix_UB_31      -0.0011818000
_diffrn_orient_matrix_UB_32      -0.0011816000
_diffrn_orient_matrix_UB_33      -0.0978342000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0922
_diffrn_reflns_av_unetI/netI     0.0495
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            32683
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.348
_diffrn_reflns_theta_min         2.815
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.925
_exptl_absorpt_correction_T_max  0.909
_exptl_absorpt_correction_T_min  0.721
_exptl_absorpt_correction_type   analytical
_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)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_density_diffrn    1.497
_exptl_crystal_description       prism
_exptl_crystal_F_000             2328
_exptl_crystal_size_max          0.5228
_exptl_crystal_size_mid          0.2115
_exptl_crystal_size_min          0.1181
_refine_diff_density_max         0.734
_refine_diff_density_min         -1.153
_refine_diff_density_rms         0.117
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.184
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     479
_refine_ls_number_reflns         4850
_refine_ls_number_restraints     204
_refine_ls_restrained_S_all      1.159
_refine_ls_R_factor_all          0.0998
_refine_ls_R_factor_gt           0.0835
_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^)+56.4217P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1537
_refine_ls_wR_factor_ref         0.1600
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4032
_reflns_number_total             4850
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b07872_si_005.cif
_cod_data_source_block           170602_lfr_0427_abs
_cod_database_code               4133010
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         c45h59b11br5n1o2
_reflns_odcompleteness_completeness 99.75
_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
 C26B-C26 = C30-C26 = C30-C29 = C29-C28 = C28-C27 = C27-C26B
 1.41 with sigma of 0.02
 C30-C26 \\sim C28-C27 \\sim C30-C29 \\sim C29-C28
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C26 \\sim C26B \\sim C27 \\sim C28 \\sim C29 \\sim C30: within 4A with sigma of
0.03 and sigma for terminal atoms of 0.06
4. Rigid body (RIGU) restrains
 C9, C22, C23, C24, C25, C21
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C3, C31, C35, C34, C33, C32
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C20, B1, B3, B2AA, B10, B2, B8, B9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C15, C16, C17, C18, C19, C14
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26B, C26, C30, C29, C28, C27, Br5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H3B)=Sof(H9B)=Sof(Br4)=Sof(Br6)=Sof(C21)=Sof(C22)=Sof(C23)=Sof(H23)=
 Sof(C24)=Sof(H24)=Sof(C25)=Sof(H25)=Sof(C31)=Sof(C32)=Sof(C33)=Sof(H33)=
 Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35)=Sof(B2AA)=Sof(H2AA)=Sof(B8)=Sof(H8)=1-
 FVAR(1)
 Sof(Br5)=Sof(C20)=Sof(H20)=Sof(C26)=Sof(C27)=Sof(C28)=Sof(H28)=Sof(C29)=
 Sof(H29)=Sof(C30)=Sof(H30)=Sof(B9)=Sof(H9)=Sof(B10)=Sof(H10)=Sof(C26B)=
 Sof(H26B)=0.5*(1-FVAR(2))
 Sof(C15)=Sof(H15)=Sof(Br3)=Sof(C1)=Sof(H1)=Sof(C14)=Sof(C16)=Sof(C17)=
 Sof(H17)=Sof(C18)=Sof(H18)=Sof(C19)=Sof(H19)=Sof(B5)=Sof(H5A)=Sof(B7)=Sof(H7A)=
 0.5*FVAR(2)
 Sof(H3A)=Sof(H9A)=Sof(Br1)=Sof(Br2)=Sof(C2)=Sof(C4)=Sof(C5)=Sof(H5)=Sof(C6)=
 Sof(H6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(C10)=Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12)=
 Sof(C13)=Sof(H13)=Sof(B4)=Sof(H4)=Sof(B6)=Sof(H6A)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C36(H36A,H36B), C38(H38A,H38B)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3A), C3(H3B), C9(H9A), C9(H9B), C15(H15), C5(H5), C6(H6), C7(H7),
 C11(H11), C12(H12), C13(H13), C17(H17), C18(H18), C19(H19), C23(H23), C24(H24),
  C25(H25), C28(H28), C29(H29), C30(H30), C33(H33), C34(H34), C35(H35),
 C26B(H26B)
6.c Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C42(H42A,H42B,H42C), C37(H37A,H37B,H37C), C39(H39A,H39B,
 H39C)
6.d Boron cage BH refined with riding coordinates:
 C1(H1), B4(H4), B5(H5A), B6(H6A), B7(H7A), C20(H20), B2AA(H2AA), B8(H8),
 B9(H9), B10(H10)
;
_shelx_res_checksum              98440
_shelx_hkl_checksum              82517
_olex2_submission_special_instructions 'No special instructions were received'