Nickel-catalyzed Cyanation of Aryl Halides and Triflates Using Acetonitrile via the C—CN Bond Cleavage Assisted by 1,4-Bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine
Ueda, Yohei; Tsujimoto, Nagataka; Yurino, Taiga; Tsurugi, Hayato; Mashima, Kazushi; Chemical Science  (2019) –; doi:10.1039/C8SC04437F

data_1550293
_publ_section_title
;
 Nickel-catalyzed Cyanation of Aryl Halides and Triflates Using
 Acetonitrile via the C---CN Bond Cleavage Assisted by
 1,4-Bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C8SC04437F
_journal_year                    2019
_chemical_absolute_configuration 'CHOOSE rm ad rmad syn or unk'
_chemical_formula_moiety         'C20 H17 Br N2 Ni O'
_chemical_formula_sum            'C20 H17 Br N2 Ni O'
_chemical_formula_weight         439.97
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_symmetry_space_group_name_Hall  'C -2yc'
_symmetry_space_group_name_H-M   'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_update_record
;
2018-06-28 deposited with the CCDC.
2018-11-26 downloaded from the CCDC.
;
_cell_angle_alpha                90.0000
_cell_angle_beta                 90.11(4)
_cell_angle_gamma                90.0000
_cell_formula_units_Z            4
_cell_length_a                   11.964(13)
_cell_length_b                   20.02(2)
_cell_length_c                   7.423(11)
_cell_measurement_reflns_used    977
_cell_measurement_temperature    113
_cell_measurement_theta_max      25.90
_cell_measurement_theta_min      3.40
_cell_volume                     1778(4)
_computing_cell_refinement       'CrystalClear-SM Expert 2.1 b45'
_computing_data_collection
'CrystalClear-SM Expert 2.1 b45 (Rigaku, 2015)'
_computing_data_reduction        'CrystalClear-SM Expert 2.1 b45'
_computing_molecular_graphics    'CrystalStructure 4.2.4'
_computing_publication_material  'CrystalStructure 4.2.4 (Rigaku, 2016)'
_computing_structure_refinement  'SHELXL Version 2016/4 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT Version 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      113
_diffrn_detector_area_resol_mean 5.814
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Rigaku XtaLAB P200'
_diffrn_measurement_method       \w
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.1996
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            21939
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.738
_diffrn_reflns_theta_min         3.384
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.355
_exptl_absorpt_correction_T_max  0.935
_exptl_absorpt_correction_T_min  0.606
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'REQAB (Rigaku, 1998)'
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.644
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       chip
_exptl_crystal_F_000             888.00
_exptl_crystal_size_max          0.080
_exptl_crystal_size_mid          0.020
_exptl_crystal_size_min          0.020
_refine_diff_density_max         1.38
_refine_diff_density_min         -0.97
_refine_ls_abs_structure_details
;
 Flack x determined using 864 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.921
_refine_ls_hydrogen_treatment    constr
_refine_ls_number_parameters     228
_refine_ls_number_reflns         4057
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.1249
_refine_ls_R_factor_gt           0.0728
_refine_ls_shift/su_max          0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w = 1/[\s^2^(Fo^2^)+(0.0992P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1620
_refine_ls_wR_factor_ref         0.1807
_reflns_Friedel_coverage         0.946
_reflns_Friedel_fraction_full    0.971
_reflns_Friedel_fraction_max     0.945
_reflns_number_gt                2441
_reflns_number_total             4057
_reflns_threshold_expression     F^2^>2.0\s(F^2^)
_cod_data_source_file            c8sc04437f2.cif
_cod_data_source_block           Ni(C6H3-4-OMe-2-Me)Br(L5)
_cod_database_code               1550293
_shelx_res_checksum              40144