Regiodivergent C-H alkynylation of 2-arylthiazoles switched by Ru<sup>II</sup> and Pd<sup>II</sup> catalysis.
Zhou, Pengfei; Liang, Xinyao; Xu, Zekun; Chen, Honggu; Wei, Zongwu; Liang, Taoyuan; Jiang, Jun; Zhang, Zhuan; Chemical communications (Cambridge, England) 60 (2024) 6679–6682; doi:10.1039/d4cc02254h

data_7133153
_publ_section_title
;
 Regiodivergent C-H alkynylation of 2-arylthiazoles switched by
 Ru<sup>II</sup> and Pd<sup>II</sup> catalysis.
;
_journal_issue                   52
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              6679
_journal_page_last               6682
_journal_paper_doi               10.1039/d4cc02254h
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C22 H29 N O S Si'
_chemical_formula_sum            'C22 H29 N O S Si'
_chemical_formula_weight         383.61
_chemical_name_systematic        xzk
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-04-19
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-04-19 deposited with the CCDC.	2024-06-04 downloaded from the CCDC.
;
_cell_angle_alpha                104.490(7)
_cell_angle_beta                 90.974(6)
_cell_angle_gamma                91.921(7)
_cell_formula_units_Z            4
_cell_length_a                   8.7980(7)
_cell_length_b                   12.4654(13)
_cell_length_c                   21.0908(14)
_cell_measurement_reflns_used    4101
_cell_measurement_temperature    293.15
_cell_measurement_theta_max      26.4310
_cell_measurement_theta_min      2.8510
_cell_volume                     2237.4(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.99a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.99a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.99a (Rigaku OD, 2023)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1213
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_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    -19.00  53.00   1.00    3.00    --   17.04 -99.00-150.00   72
  2  \w     41.00  68.00   1.00    3.00    --   17.04 178.00 -30.00   27
  3  \w    -51.00  36.00   1.00    3.00    --   17.04 -57.00 -30.00   87
  4  \w    -21.00  86.00   1.00    3.00    --   17.04  19.00 150.00  107
  5  \w    -37.00   9.00   1.00    3.00    --  -17.59 -77.00-120.00   46
  6  \w    -23.00  11.00   1.00    3.00    --  -17.59 -77.00   0.00   34
  7  \w    -38.00   0.00   1.00    3.00    --  -17.59 -77.00  90.00   38
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0341764000
_diffrn_orient_matrix_UB_12      0.0510855000
_diffrn_orient_matrix_UB_13      0.0009282000
_diffrn_orient_matrix_UB_21      0.0338978000
_diffrn_orient_matrix_UB_22      0.0231619000
_diffrn_orient_matrix_UB_23      0.0314159000
_diffrn_orient_matrix_UB_31      0.0647642000
_diffrn_orient_matrix_UB_32      0.0176940000
_diffrn_orient_matrix_UB_33      -0.0148179000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0452
_diffrn_reflns_av_unetI/netI     0.0814
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            17857
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.373
_diffrn_reflns_theta_min         2.268
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.208
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83322
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.99a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light black'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.139
_exptl_crystal_description       block
_exptl_crystal_F_000             824
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.296
_refine_diff_density_min         -0.285
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     483
_refine_ls_number_reflns         9131
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.1493
_refine_ls_R_factor_gt           0.0671
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0931P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1786
_refine_ls_wR_factor_ref         0.2381
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3851
_reflns_number_total             9131
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc02254h2.cif
_cod_data_source_block           exp_14226_auto
_cod_depositor_comments
'Adding full bibliography for 7133152--7133153.cif.'
_cod_database_code               7133153
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.998
_shelx_estimated_absorpt_t_min   0.994
_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. Rigid bond restraints
 C2, C1, O1, C24, C23
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
3.a Ternary CH refined with riding coordinates:
 C39(H39), C42(H42), C36(H36), C20(H20), C17(H17), C14(H14)
3.b Aromatic/amide H refined with riding coordinates:
 C29(H29), C32(H32), C28(H28), C27(H27), C26(H26), C5(H5), C4(H4), C7(H7),
 C10(H10), C8(H8)
3.c Idealised Me refined as rotating group:
 C40(H40a,H40b,H40c), C23(H23a,H23b,H23c), C41(H41a,H41b,H41c), C43(H43a,H43b,
 H43c), C44(H44a,H44b,H44c), C37(H37a,H37b,H37c), C38(H38a,H38b,H38c), C1(H1a,
 H1b,H1c), C22(H22a,H22b,H22c), C21(H21a,H21b,H21c), C18(H18a,H18b,H18c),
 C19(H19a,H19b,H19c), C15(H15a,H15b,H15c), C16(H16a,H16b,H16c)
;
_shelx_res_checksum              3502
_shelx_hkl_checksum              80951
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.388
_oxdiff_exptl_absorpt_empirical_full_min 0.791