Reductive desymmetric silylation of biaryl bis(triflates) enabled by a chiral nickel/picolinamide complex.
Chen, Zhe; Zhang, Junjie; Wang, Chuan; Chemical science 17 (2026) 6710–6716; doi:10.1039/d5sc09250g

data_1576493
_publ_section_title
;
 Reductive desymmetric silylation of biaryl bis(triflates) enabled by a
 chiral nickel/picolinamide complex.
;
_journal_issue                   13
_journal_name_full               'Chemical science'
_journal_page_first              6710
_journal_page_last               6716
_journal_paper_doi               10.1039/d5sc09250g
_journal_volume                  17
_journal_year                    2026
_chemical_absolute_configuration rmad
_chemical_formula_moiety         '2(C27 H29 F3 O3 S Si)'
_chemical_formula_sum            'C54 H58 F6 O6 S2 Si2'
_chemical_formula_weight         1037.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-01-21
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-05-19 deposited with the CCDC.	2026-02-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.373(9)
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   9.7587(16)
_cell_length_b                   14.161(3)
_cell_length_c                   9.8462(15)
_cell_measurement_reflns_used    6082
_cell_measurement_temperature    170.00
_cell_measurement_theta_max      54.727
_cell_measurement_theta_min      4.000
_cell_volume                     1329.1(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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      170.00
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0774
_diffrn_reflns_av_unetI/netI     0.0775
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            12173
_diffrn_reflns_point_group_measured_fraction_full 0.935
_diffrn_reflns_point_group_measured_fraction_max 0.921
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         55.089
_diffrn_reflns_theta_min         3.999
_diffrn_source_current           3.57
_diffrn_source_power             0.2491146
_diffrn_source_voltage           69.78
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.254
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.1796
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1795 before and 0.1082 after correction.
The Ratio of minimum to maximum transmission is 0.2392.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.296
_exptl_crystal_description       block
_exptl_crystal_F_000             544
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.606
_refine_diff_density_min         -0.465
_refine_diff_density_rms         0.077
_refine_ls_abs_structure_details
;
 Flack x determined using 1792 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.031(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     321
_refine_ls_number_reflns         4670
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0616
_refine_ls_R_factor_gt           0.0590
_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^)+(0.1112P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1538
_refine_ls_wR_factor_ref         0.1598
_reflns_Friedel_coverage         0.794
_reflns_Friedel_fraction_full    0.876
_reflns_Friedel_fraction_max     0.852
_reflns_number_gt                4405
_reflns_number_total             4670
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09250g2.cif
_cod_data_source_block           250121cz
_cod_depositor_comments
'Adding full bibliography for 1576493--1576494.cif.'
_cod_original_cell_volume        1329.0(4)
_cod_database_code               1576493
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.940
_shelx_estimated_absorpt_t_min   0.815
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C8(H8), C9(H9), C11(H11), C14(H14), C15(H15),
 C16(H16), C17(H17), C18(H18), C25(H25)
2.b X=CH2 refined with riding coordinates:
 C26(H26A,H26B)
2.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21B,H21A,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              68291
_shelx_hkl_checksum              1871
_olex2_submission_special_instructions 'No special instructions were received'