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_4518085
_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_formula_moiety         'C38 H52 N2 O2 Si2, C H2 Cl2, 0.83(H2 O)'
_chemical_formula_sum            'C39 H55.66 Cl2 N2 O2.83 Si2'
_chemical_formula_weight         724.87
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2020-08-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                88.9580(10)
_cell_angle_beta                 84.3380(10)
_cell_angle_gamma                80.0730(10)
_cell_formula_units_Z            4
_cell_length_a                   7.4568(2)
_cell_length_b                   20.0275(5)
_cell_length_c                   27.8489(7)
_cell_measurement_reflns_used    9993
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      78.54
_cell_measurement_theta_min      2.75
_cell_volume                     4076.73(18)
_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  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.966
_diffrn_measurement_device_type  'Bruker D8 Venture PHOTON II CPAD'
_diffrn_measurement_method       'omega scans'
_diffrn_radiation_monochromator  mirrors
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0649
_diffrn_reflns_av_unetI/netI     0.0509
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            79934
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         79.950
_diffrn_reflns_theta_min         2.239
_diffrn_source                   'INCOATEC Imus micro-focus source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.273
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7829
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1118 before and 0.0785 after correction.
The Ratio of minimum to maximum transmission is 0.7829.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.181
_exptl_crystal_description       plate
_exptl_crystal_F_000             1553
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.797
_refine_diff_density_min         -0.647
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     984
_refine_ls_number_reflns         17212
_refine_ls_number_restraints     299
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0713
_refine_ls_R_factor_gt           0.0592
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0742P)^2^+4.4438P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1510
_refine_ls_wR_factor_ref         0.1624
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14274
_reflns_number_total             17212
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c03207_si_008.cif
_cod_data_source_block           184
_cod_database_code               4518085
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.935
_shelx_estimated_absorpt_t_min   0.521
_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, All O(H,H) groups
2. Restrained distances
 Cl3-C111 = Cl4-C111 = C131-Cl7 = Cl8-C131
 1.75 with sigma of 0.02
 O142-H14B = O142-H14A = O141-H14C = O141-H14D
 0.86 with sigma of 0.02
 C81B-C80B = C81A-C80A = C82A-C80A = C82B-C80B
 1.53 with sigma of 0.005
 C79B-C77B = C79A-C77A = C78B-C77B = C78A-C77A
 1.53 with sigma of 0.005
 C29_$1-Cl4
 -3.45 with sigma of 0.01
 Cl3-Cl4 = Cl8-Cl7
 2.88 with sigma of 0.04
 H14A-H14B = H14C-H14D
 1.39 with sigma of 0.04
 C82A-C81A = C82B-C81B
 2.49 with sigma of 0.01
 C79B-C78B = C79A-C78A
 2.49 with sigma of 0.01
 Si73-C80A \\sim Si73-C80B
 with sigma of 0.005
 Si73-C77B \\sim Si73-C77A
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Cl6 \\sim C121 \\sim Cl5 \\sim Cl8 \\sim C131 \\sim Cl7: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08
Cl4 \\sim C111 \\sim Cl3 \\sim C101 \\sim Cl1 \\sim Cl2: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C82A \\sim C82B \\sim C80B \\sim C80A \\sim C81A \\sim C81B: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C78B \\sim C77B \\sim C79B \\sim C78A \\sim C79A: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08
Uanis(C131) = Uanis(Cl5)
Uanis(C111) = Uanis(C101)
Uanis(C81B) = Uanis(C81A)
Uanis(C80B) = Uanis(C80A)
Uanis(C78B) = Uanis(C78A)
4. Rigid body (RIGU) restrains
 Cl8, C131, Cl7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl4, C111, Cl3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C82A, C80A, C81A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C82B, C80B, C81B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C78A, C77A, C79A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C78B, C77B, C79B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C77B)=Sof(H77B)=Sof(C78B)=Sof(H78D)=Sof(H78E)=Sof(H78F)=Sof(C79B)=
 Sof(H79D)=Sof(H79E)=Sof(H79F)=Sof(C80B)=Sof(H80B)=Sof(C81B)=Sof(H81D)=
 Sof(H81E)=Sof(H81F)=Sof(C82B)=Sof(H82D)=Sof(H82E)=Sof(H82F)=1-FVAR(1)
 Sof(C77A)=Sof(H77A)=Sof(C78A)=Sof(H78A)=Sof(H78B)=Sof(H78C)=Sof(C79A)=
 Sof(H79A)=Sof(H79B)=Sof(H79C)=Sof(C80A)=Sof(H80A)=Sof(C81A)=Sof(H81A)=
 Sof(H81B)=Sof(H81C)=Sof(C82A)=Sof(H82A)=Sof(H82B)=Sof(H82C)=FVAR(1)
 Fixed Sof: C101(0.8) H10A(0.8) H10B(0.8) Cl1(0.8) Cl2(0.8) C121(0.86)
 H12A(0.86) H12B(0.86) Cl5(0.86) Cl6(0.86) C131(0.14) H13A(0.14) H13B(0.14)
 Cl7(0.14) Cl8(0.14) C111(0.2) H11A(0.2) H11B(0.2) Cl3(0.2) Cl4(0.2) O142(0.8)
 H14A(0.8) H14B(0.8) O141(0.86) H14C(0.86) H14D(0.86)
6.a Ternary CH refined with riding coordinates:
 C24(H24), C27(H27), C30(H30), C36(H36), C39(H39), C42(H42), C74(H74),
 C77A(H77A), C80A(H80A), C77B(H77B), C80B(H80B), C86(H86), C89(H89), C92(H92)
6.b Secondary CH2 refined with riding coordinates:
 C101(H10A,H10B), C121(H12A,H12B), C131(H13A,H13B), C111(H11A,H11B)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C13(H13), C15(H15), C16(H16),
 C17(H17), C18(H18), C53(H53), C54(H54), C55(H55), C56(H56), C59(H59), C63(H63),
  C65(H65), C66(H66), C67(H67), C68(H68)
6.d Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C37(H37A,H37B,H37C), C38(H38A,
 H38B,H38C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C43(H43A,H43B,H43C),
 C44(H44A,H44B,H44C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C), C78A(H78A,H78B,
 H78C), C79A(H79A,H79B,H79C), C81A(H81A,H81B,H81C), C82A(H82A,H82B,H82C),
 C78B(H78D,H78E,H78F), C79B(H79D,H79E,H79F), C81B(H81D,H81E,H81F), C82B(H82D,
 H82E,H82F), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C90(H90A,H90B,H90C),
 C91(H91A,H91B,H91C), C93(H93A,H93B,H93C), C94(H94A,H94B,H94C)
;
_shelx_res_checksum              473
_shelx_hkl_checksum              93761
_olex2_submission_special_instructions 'No special instructions were received'