Facilitating Ir-Catalyzed C–H Alkynylation with Electrochemistry: Anodic Oxidation-Induced Reductive Elimination
Ye, Xiaohan; Wang, Chenhuan; Zhang, Shuyao; Wei, Jingwen; Shan, Chuan; Wojtas, Lukasz; Xie, Yan; Shi, Xiaodong; ACS Catalysis  (2020) 11693–11699; doi:10.1021/acscatal.0c03207

data_4518086
_publ_section_title
;
 Facilitating Ir-Catalyzed C--H Alkynylation with Electrochemistry: Anodic
 Oxidation-Induced Reductive Elimination
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              11693
_journal_page_last               11699
_journal_paper_doi               10.1021/acscatal.0c03207
_journal_year                    2020
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C26 H31 N O Si'
_chemical_formula_sum            'C26 H31 N O Si'
_chemical_formula_weight         401.63
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_symmetry_Int_Tables_number      29
_atom_sites_solution_primary     iterative
_audit_creation_date             2020-06-28
_audit_creation_method
;
Olex2 1.2
(compiled Apr  3 2018 11:26:26 for OlexSys, GUI svn.r5486)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.9365(9)
_cell_length_b                   11.3131(4)
_cell_length_c                   8.3785(3)
_cell_measurement_reflns_used    9129
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      79.63
_cell_measurement_theta_min      3.54
_cell_volume                     2363.65(15)
_computing_cell_refinement       'SAINT V8.40A (?, 2016)'
_computing_data_reduction        'SAINT V8.40A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.9740
_diffrn_measured_fraction_theta_max 0.9740
_diffrn_measurement_device_type  'Bruker D8 Venture PHOTON II CPAD'
_diffrn_measurement_method       'omega scans'
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0409
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            44611
_diffrn_reflns_theta_full        79.8041
_diffrn_reflns_theta_max         79.80
_diffrn_reflns_theta_min         3.54
_exptl_absorpt_coefficient_mu    0.982
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.6125
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1636 before and 0.0694 after correction.
The Ratio of minimum to maximum transmission is 0.6125.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.1285
_exptl_crystal_description       block
_exptl_crystal_F_000             867.2393
_exptl_crystal_size_max          0.095
_exptl_crystal_size_mid          0.057
_exptl_crystal_size_min          0.055
_refine_diff_density_max         0.2869
_refine_diff_density_min         -0.2550
_refine_diff_density_rms         0.0365
_refine_ls_abs_structure_details
'Flack, H. D. (1983). Acta Cryst. A39, 876-881.'
_refine_ls_abs_structure_Flack   0.098(15)
_refine_ls_d_res_high            0.7833
_refine_ls_d_res_low             12.4682
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.0695
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    72
_refine_ls_number_parameters     311
_refine_ls_number_reflns         5021
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.0686
_refine_ls_R_factor_all          0.0274
_refine_ls_R_factor_gt           0.0274
_refine_ls_shift/su_max          0.2044
_refine_ls_shift/su_mean         0.0094
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0513P)^2^+0.2793P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0758
_refine_ls_wR_factor_ref         0.0758
_reflns_Friedel_coverage         0.947
_reflns_limit_h_max              31
_reflns_limit_h_min              -31
_reflns_limit_k_max              14
_reflns_limit_k_min              -14
_reflns_limit_l_max              10
_reflns_limit_l_min              -10
_reflns_number_gt                5016
_reflns_number_total             5021
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            cs0c03207_si_007.cif
_cod_data_source_block           12_126
_cod_original_sg_symbol_Hall     ' P 2c -2ac'
_cod_database_code               4518086
_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. Restrained distances
 C25B-C21 = C26B-C21 = C27A-C22 = C28A-C22
 1.52 with sigma of 0.01
3. Rigid body (RIGU) restrains
 C22, C27A, C28A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21, C25B, C26B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(H21a)=Sof(C25B)=Sof(H25d)=Sof(H25e)=Sof(H25f)=Sof(C26B)=Sof(H26d)=
 Sof(H26e)=Sof(H26f)=1-FVAR(1)
 Sof(H21)=Sof(C25A)=Sof(H25a)=Sof(H25b)=Sof(H25c)=Sof(C26A)=Sof(H26a)=
 Sof(H26b)=Sof(H26c)=FVAR(1)
 Sof(H22a)=Sof(C27B)=Sof(H27d)=Sof(H27e)=Sof(H27f)=Sof(C28B)=Sof(H28d)=
 Sof(H28e)=Sof(H28f)=1-FVAR(2)
 Sof(H22)=Sof(C27A)=Sof(H27a)=Sof(H27b)=Sof(H27c)=Sof(C28A)=Sof(H28a)=
 Sof(H28b)=Sof(H28c)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C20(H20), C21(H21a), C22(H22)
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C10(H10), C16(H16), C17(H17),
 C18(H18), C19(H19)
5.c Idealised Me refined as rotating group:
 C23(H23a,H23b,H23c), C24(H24a,H24b,H24c), C27A(H27a,H27b,H27c), C28A(H28a,
 H28b,H28c), C25B(H25d,H25e,H25f), C26B(H26d,H26e,H26f)
;
_olex2_submission_special_instructions 'No special instructions were received'