Nickel-Catalysed Direct C2-Arylation of N-Heterocyclic Carbene
Ghadwal, Rajendra S.; Ho, Nga Kim; Neumann, Beate; Stammler, Georg; Menezes da Silva, Vitor Hugo; Watanabe, Daniel; Braga, Ataualpa A. C.; Dalton Trans.  (2017) –; doi:10.1039/C7DT03099A

data_7044015
_publ_section_title
;
 Nickel-Catalysed Direct C2-Arylation of N-Heterocyclic Carbene
;
_journal_name_full               'Dalton Trans.'
_journal_paper_doi               10.1039/C7DT03099A
_journal_year                    2017
_chemical_formula_moiety         'C34 H43 N2, Br'
_chemical_formula_sum            'C34 H43 Br N2'
_chemical_formula_weight         559.61
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-01-24
_audit_creation_method
;
  Olex2 1.2-ac2
  (compiled 2012.03.27 svn.r2268, GUI svn.r4156)
;
_audit_update_record
;
2017-06-28 deposited with the CCDC.
2017-08-22 downloaded from the CCDC.
;
_cell_angle_alpha                110.1753(14)
_cell_angle_beta                 102.3785(13)
_cell_angle_gamma                96.7444(12)
_cell_formula_units_Z            4
_cell_length_a                   12.65346(19)
_cell_length_b                   15.1670(2)
_cell_length_c                   18.3140(3)
_cell_measurement_reflns_used    27833
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.2620
_cell_measurement_theta_min      3.1400
_cell_volume                     3151.40(9)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3114
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.9995
_diffrn_measured_fraction_theta_max 0.9972
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -68.00  30.00   1.00    3.50    --  -38.50  77.00 -30.00   98
  2  \w   -105.00  -6.00   1.00    3.50    --  -38.50 -19.00 -30.00   99
  3  \w    -58.00  33.00   1.00    3.50    --  -38.50  38.00  90.00   91
  4  \w   -109.00 -18.00   1.00    3.50    --  -38.50 -38.00 -90.00   91
  5  \w      2.00  79.00   1.00    3.50    --   43.45 -99.00 150.00   77
  6  \w     13.00  89.00   1.00    3.50    --   43.45  77.00-180.00   76
  7  \w     13.00  64.00   1.00    3.50    --   43.45  77.00   0.00   51
  8  \w     13.00  76.00   1.00    3.50    --   43.45  77.00 -90.00   63
  9  \w     18.00  44.00   1.00    3.50    --   43.45  57.00-150.00   26
 10  \w     14.00 110.00   1.00    3.50    --   43.45  77.00  90.00   96
 11  \w     61.00  92.00   1.00    3.50    --   43.45  57.00-150.00   31
 12  \w     18.00  83.00   1.00    3.50    --   43.45  57.00  60.00   65
 13  \w     58.00 108.00   1.00    3.50    --   43.45 178.00 -30.00   50
 14  \w     81.00 178.00   1.00   14.00    --  111.00  77.00-150.00   97
 15  \w     85.00 170.00   1.00   14.00    --  111.00  61.00 120.00   85
 16  \w     88.00 167.00   1.00   14.00    --  111.00  49.00 -93.44   79
 17  \w     45.00 106.00   1.00   14.00    --  111.00 -77.00-180.00   61
 18  \w     81.00 107.00   1.00   14.00    --  111.00  77.00 -30.00   26
 19  \w     83.00 109.00   1.00   14.00    --  111.00  70.00  -7.86   26
 20  \w     84.00 177.00   1.00   14.00    --  111.00  63.00 155.69   93
 21  \w     85.00 111.00   1.00   14.00    --  111.00  61.00  60.00   26
 22  \w     41.00 122.00   1.00   14.00    --  111.00-125.00-150.00   81
 23  \w     82.00 107.00   1.00   14.00    --  111.00  77.00-120.00   25
 24  \w     81.00 107.00   1.00   14.00    --  111.00  77.00 120.00   26
 25  \w     44.00 134.00   1.00   14.00    --  111.00 -61.00  30.00   90
 26  \w     85.00 111.00   1.00   14.00    --  111.00  61.00-180.00   26
 27  \w     85.00 177.00   1.00   14.00    --  111.00  61.00 -30.00   92
 28  \w     85.00 163.00   1.00   14.00    --  111.00  61.00  30.00   78
 29  \w    122.00 176.00   1.00   14.00    --  111.00  77.00  90.00   54
 30  \w     81.00 116.00   1.00   14.00    --  111.00  77.00  90.00   35
 31  \w    133.00 171.00   1.00   14.00    --  111.00  77.00-180.00   38
 32  \w     81.00 130.00   1.00   14.00    --  111.00  77.00-180.00   49
 33  \w     82.00 109.00   1.00   14.00    --  111.00  74.00 177.01   27
 34  \w     96.00 136.00   1.00   14.00    --  111.00 -61.00-150.00   40
 35  \w     85.00 111.00   1.00   14.00    --  111.00  61.00-120.00   26
 36  \w     44.00  92.00   1.00   14.00    --  111.00 -61.00-150.00   48
 37  \w     85.00 111.00   1.00   14.00    --  111.00  61.00 150.00   26
 38  \w     57.00 122.00   1.00   14.00    --  111.00-125.00  30.00   65
 39  \w     85.00 153.00   1.00   14.00    --  111.00  61.00-150.00   68
 40  \w     85.00 178.00   1.00   14.00    --  111.00  61.00 -90.00   93
 41  \w     81.00 107.00   1.00   14.00    --  111.00  77.00  30.00   26
 42  \w     81.00 107.00   1.00   14.00    --  111.00  77.00 -60.00   26
 43  \w     86.00 111.00   1.00   14.00    --  111.00  61.00  90.00   25
 44  \w     85.00 156.00   1.00   14.00    --  111.00  61.00 -60.00   71
 45  \w     81.00 170.00   1.00   14.00    --  111.00  77.00   0.00   89
 46  \w     81.00 177.00   1.00   14.00    --  111.00  77.00  60.00   96
 47  \w     81.00 107.00   1.00   14.00    --  111.00  77.00 150.00   26
 48  \w    142.00 168.00   1.00   14.00    --  111.00  77.00-120.00   26
 49  \w     90.00 118.00   1.00   14.00    --  111.00-121.00 157.00   28
 50  \w     63.00 109.00   1.00   14.00    --  111.00 -94.00 -90.00   46
 51  \w     32.00 106.00   1.00   14.00    --  111.00 -94.00  30.00   74
 52  \w     81.00 107.00   1.00   14.00    --  111.00  76.00-158.80   26
 53  \w     81.00 107.00   1.00   14.00    --  111.00  77.00 -90.00   26
 54  \w     84.00 176.00   1.00   14.00    --  111.00  63.00  39.99   92
 55  \w     83.00 110.00   1.00   14.00    --  111.00  67.00 -61.94   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0561159000
_diffrn_orient_matrix_UB_12      0.0701487000
_diffrn_orient_matrix_UB_13      0.0877659000
_diffrn_orient_matrix_UB_21      -0.0827323000
_diffrn_orient_matrix_UB_22      -0.0525470000
_diffrn_orient_matrix_UB_23      0.0296796000
_diffrn_orient_matrix_UB_31      0.0790652000
_diffrn_orient_matrix_UB_32      -0.0675387000
_diffrn_orient_matrix_UB_33      0.0098311000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0372
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            61446
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.55
_diffrn_reflns_theta_min         2.67
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.933
_exptl_absorpt_correction_T_max  0.915
_exptl_absorpt_correction_T_min  0.655
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.179
_exptl_crystal_description       plate
_exptl_crystal_F_000             1184
_exptl_crystal_size_max          0.161
_exptl_crystal_size_mid          0.066
_exptl_crystal_size_min          0.023
_refine_diff_density_max         0.804
_refine_diff_density_min         -1.437
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     689
_refine_ls_number_reflns         12465
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0512
_refine_ls_R_factor_gt           0.0447
_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^)+(0.0816P)^2^+1.6735P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1301
_refine_ls_wR_factor_ref         0.1354
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10772
_reflns_number_total             12465
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt03099a2.cif
_cod_data_source_block           compound_3b
_cod_original_cell_volume        3151.39(9)
_cod_database_code               7044015
_chemical_oxdiff_formula         'C34 H43 Br N2'
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_date_sample_data_collection 2017-01-22
_olex2_date_sample_submission    1484780400
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(Br2A) = Uanis(Br2B)
3. Others
 Sof(Br2B)=1-FVAR(1)
 Sof(Br2A)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C10(H10), C13(H13), C22(H22), C25(H25), C44(H44), C47(H47), C56(H56), C59(H59)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C7(H7), C8(H8), C18(H18), C19(H19), C20(H20),
 C29(H29), C30(H30), C32(H32), C33(H33), C36(H36), C37(H37), C40(H40), C41(H41),
  C42(H42), C52(H52), C53(H53), C54(H54), C63(H63), C64(H64), C66(H66), C67(H67)
4.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C15(H15A,H15B,
 H15C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,
 H27B,H27C), C34(H34A,H34B,H34C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C),
 C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C57(H57A,H57B,H57C), C58(H58A,H58B,
 H58C), C60(H60A,H60B,H60C), C61(H61A,H61B,H61C), C68(H68A,H68B,H68C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.178
_oxdiff_exptl_absorpt_empirical_full_min 0.891
_shelx_res_checksum              74194
_shelx_shelxl_version_number     2016/4