Nickel-catalyzed cross-electrophile-coupling of thioesters with alkyl bromides to form ketones under mechanochemical conditions.
Lindenmaier, Ivo H.; Richter, Robert C.; Renz, Liesa; Vochezer, Mattis T.; Schier, Marius; Faßnacht, Pascal; Ströbele, Markus; Fleischer, Ivana; Chemical communications (Cambridge, England) 62 (2026) 5284–5288; doi:10.1039/d6cc00297h

data_7135369
_publ_section_title
;
 Nickel-catalyzed cross-electrophile-coupling of thioesters with alkyl
 bromides to form ketones under mechanochemical conditions.
;
_journal_issue                   18
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              5284
_journal_page_last               5288
_journal_paper_doi               10.1039/d6cc00297h
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety         'C31 H33 F N2 Ni O S'
_chemical_formula_sum            'C31 H33 F N2 Ni O S'
_chemical_formula_weight         559.378
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_Int_Tables_number      14
_atom_sites_solution_primary     dual
_audit_creation_date             2025-09-24
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-09-24 deposited with the CCDC.	2026-02-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.574(1)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.9419(1)
_cell_length_b                   12.3816(1)
_cell_length_c                   18.7832(2)
_cell_measurement_reflns_used    15909
_cell_measurement_temperature    149.99(11)
_cell_measurement_theta_max      79.6760
_cell_measurement_theta_min      4.2440
_cell_volume                     2774.48(4)
_computing_cell_refinement       'CrysAlisPro 1.171.44.118a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.115a 64-bit (release 23-06-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.118a (Rigaku OD, 2025)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.0000
_diffrn_measured_fraction_theta_max 0.9972
_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    -73.00  -1.00   0.50    8.00    --  -49.87 110.00 -55.00  144
  2  \w     33.00  77.00   0.50    8.00    --   49.87-110.00-150.00   88
  3  \w    -74.00 -49.00   0.50   40.00    --  -90.00 110.00 -55.00   50
  4  \w   -146.00-121.00   0.50   40.00    --  -90.00-110.00-150.00   50
  5  \w     58.00 108.00   0.50   40.00    --  111.50-110.00-150.00  100
  6  \w    116.00 141.00   0.50   40.00    --  111.50 110.00 -55.00   50
  7  \w    -60.00  20.00   0.50    8.00    --  -49.87  57.00 -90.00  160
  8  \w    -24.00   2.00   0.50    8.00    --  -49.87  19.00 150.00   52
  9  \w   -119.00 -73.00   0.50    8.00    --  -49.87-125.00  90.00   92
 10  \w    -18.00  16.00   0.50    8.00    --  -49.87  19.00-180.00   68
 11  \w   -113.00 -37.00   0.50    8.00    --  -49.87 -77.00  30.00  152
 12  \w    -25.00   4.00   0.50    8.00    --  -49.87  19.00 -30.00   58
 13  \w   -120.00 -95.00   0.50    8.00    --  -49.87-125.00 -90.00   50
 14  \w   -112.00 -75.00   0.50    8.00    --  -49.87-125.00   0.00   74
 15  \w    -22.00   5.00   0.50    8.00    --   49.87 -19.00 -30.00   54
 16  \w    -48.00 -18.00   0.50   40.00    --  -90.00  45.00-120.00   60
 17  \w    -51.00 -25.00   0.50   40.00    --  -90.00  45.00 150.00   52
 18  \w    -51.00 -24.00   0.50   40.00    --  -90.00  45.00   0.00   54
 19  \w   -137.00-104.00   0.50   40.00    --  -90.00   0.00  30.00   66
 20  \w     79.00 105.00   0.50   40.00    --  111.50 -94.00-150.00   52
 21  \w    134.00 161.00   0.50   40.00    --  111.50  61.00  30.00   54
 22  \w     42.00  71.00   0.50   40.00    --  111.50 -94.00-150.00   58
 23  \w     85.00 111.00   0.50   40.00    --  111.50 -86.00 -25.53   52
 24  \w     83.00 110.00   0.50   40.00    --  111.50-125.00-120.00   54
 25  \w     80.00 106.00   0.50   40.00    --  111.50 -94.00 -30.00   52
 26  \w     41.00  71.00   0.50   40.00    --  111.50 -61.00 -30.00   60
 27  \w     43.00  76.00   0.50   40.00    --  111.50 -94.00 -30.00   66
 28  \w     67.00 113.00   0.50   40.00    --  111.50   0.00   0.00   92
 29  \w     54.00  80.00   0.50   40.00    --  111.50-125.00 -90.00   52
 30  \w     81.00 111.00   0.50   40.00    --  111.50-125.00 -90.00   60
 31  \w     68.00 101.00   0.50   40.00    --  111.50 -77.00-150.00   66
 32  \w     99.00 129.00   0.50   40.00    --  111.50  61.00  30.00   60
 33  \w     41.00  70.00   0.50   40.00    --  111.50 -94.00-180.00   58
 34  \w     55.00  89.00   0.50   40.00    --  111.50 -77.00   0.00   68
 35  \w    104.00 130.00   0.50   40.00    --  111.50  61.00-150.00   52
 36  \w    138.00 168.00   0.50   40.00    --  111.50  61.00-150.00   60
 37  \w     63.00  88.00   0.50   40.00    --  111.50   0.00 -90.00   50
 38  \w     44.00  70.00   0.50   40.00    --  111.50 -94.00-120.00   52
 39  \w     93.00 120.00   0.50   40.00    --  111.50 -87.00  59.94   54
 40  \w     85.00 110.00   0.50   40.00    --  111.50-125.00 150.00   50
 41  \w     41.00  68.00   0.50   40.00    --  111.50 -61.00-150.00   54
 42  \w     41.00  75.00   0.50   40.00    --  111.50 -94.00  30.00   68
 43  \w     58.00 107.00   0.50   40.00    --  111.50-125.00-150.00   98
 44  \w     59.00  85.00   0.50   40.00    --  111.50 -87.00  59.94   52
 45  \w     80.00 106.00   0.50   40.00    --  111.50 -94.00  30.00   52
 46  \w    123.00 168.00   0.50   40.00    --  111.50  45.00 -60.00   90
 47  \w    104.00 134.00   0.50   40.00    --  111.50  61.00  90.00   60
 48  \w     80.00 106.00   0.50   40.00    --  111.50 -94.00-120.00   52
 49  \w    103.00 129.00   0.50   40.00    --  111.50 125.00 150.00   52
 50  \w     80.00 105.00   0.50   40.00    --  111.50 -94.00  60.00   50
 51  \w    118.00 166.00   0.50   40.00    --  111.50 125.00  30.00   96
 52  \w     48.00  73.00   0.50   40.00    --  111.50-125.00-120.00   50
 53  \w     84.00 118.00   0.50   40.00    --  111.50   0.00  60.00   68
 54  \w     63.00  89.00   0.50   40.00    --  111.50   0.00 -60.00   52
 55  \w    125.00 176.00   0.50   40.00    --  111.50  30.00 -90.00  102
 56  \w     53.00  79.00   0.50   40.00    --  111.50-125.00 150.00   52
 57  \w     81.00 106.00   0.50   40.00    --  111.50 -77.00 120.00   50
 58  \w    119.00 157.00   0.50   40.00    --  111.50  30.00-120.00   76
 59  \w     92.00 122.00   0.50   40.00    --  111.50  77.00 150.00   60
 60  \w    134.00 160.00   0.50   40.00    --  111.50  77.00 150.00   52
 61  \w     93.00 176.00   0.50   40.00    --  111.50  77.00  30.00  166
 62  \w     81.00 106.00   0.50   40.00    --  111.50 -94.00-180.00   50
 63  \w     80.00 106.00   0.50   40.00    --  111.50 -94.00   0.00   52
 64  \w     47.00 110.00   0.50   40.00    --  111.50-125.00  90.00  126
 65  \w    106.00 178.00   0.50   40.00    --  111.50  45.00-120.00  144
 66  \w    138.00 171.00   0.50   40.00    --  111.50  45.00  90.00   66
 67  \w     43.00 103.00   0.50   40.00    --  111.50 -77.00-120.00  120
 68  \w     57.00  83.00   0.50   40.00    --  111.50 -77.00 -90.00   52
 69  \w    110.00 178.00   0.50   40.00    --  111.50  30.00-180.00  136
 70  \w     58.00  91.00   0.50   40.00    --  111.50-125.00-180.00   66
 71  \w     80.00 105.00   0.50   40.00    --  111.50 -94.00 -90.00   50
 72  \w     73.00 105.00   0.50   40.00    --  111.50 -94.00 120.00   64
 73  \w     57.00  83.00   0.50   40.00    --  111.50 -77.00  60.00   52
 74  \w    100.00 128.00   0.50   40.00    --  111.50  61.00   0.00   56
 75  \w     92.00 117.00   0.50   40.00    --  111.50  77.00  60.00   50
 76  \w    137.00 178.00   0.50   40.00    --  111.50  77.00  60.00   82
 77  \w     79.00 104.00   0.50   40.00    --  111.50 -77.00 -30.00   50
 78  \w     41.00  71.00   0.50   40.00    --  111.50 -77.00 -30.00   60
 79  \w     99.00 154.00   0.50   40.00    --  111.50  61.00 120.00  110
 80  \w     42.00  68.00   0.50   40.00    --  111.50 -77.00-180.00   52
 81  \w     41.00  70.00   0.50   40.00    --  111.50 -94.00 -60.00   58
 82  \w    112.00 177.00   0.50   40.00    --  111.50  30.00 -30.00  130
 83  \w    150.00 176.00   0.50   40.00    --  111.50  30.00 120.00   52
 84  \w     49.00  74.00   0.50   40.00    --  111.50-125.00 -60.00   50
 85  \w     60.00  95.00   0.50   40.00    --  111.50-125.00   0.00   70
 86  \w     84.00 109.00   0.50   40.00    --  111.50-125.00  30.00   50
 87  \w    113.00 139.00   0.50   40.00    --  111.50  15.00 -30.00   52
 88  \w    104.00 143.00   0.50   40.00    --  111.50  45.00  30.00   78
 89  \w    106.00 137.00   0.50   40.00    --  111.50  61.00  60.00   62
 90  \w     98.00 142.00   0.50   40.00    --  111.50  61.00 150.00   88
 91  \w    131.00 162.00   0.50   40.00    --  111.50 125.00 -30.00   62
 92  \w    140.00 166.00   0.50   40.00    --  111.50 125.00 120.00   52
 93  \w     60.00 105.00   0.50   40.00    --  111.50 -97.00 -48.91   90
 94  \w     92.00 119.00   0.50   40.00    --  111.50  77.00 120.00   54
 95  \w    137.00 162.00   0.50   40.00    --  111.50  77.00 120.00   50
 96  \w     47.00  72.00   0.50   40.00    --  111.50 -84.00 165.09   50
 97  \w     84.00 109.00   0.50   40.00    --  111.50 -84.00 165.09   50
 98  \w     44.00  69.00   0.50   40.00    --  111.50 -61.00  60.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0382887000
_diffrn_orient_matrix_UB_12      0.0280692000
_diffrn_orient_matrix_UB_13      -0.0772154000
_diffrn_orient_matrix_UB_21      -0.0184078000
_diffrn_orient_matrix_UB_22      0.1182533000
_diffrn_orient_matrix_UB_23      0.0221586000
_diffrn_orient_matrix_UB_31      0.1219268000
_diffrn_orient_matrix_UB_32      0.0266447000
_diffrn_orient_matrix_UB_33      -0.0170004000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0304
_diffrn_reflns_av_unetI/netI     0.0155
_diffrn_reflns_Laue_measured_fraction_full 1.0000
_diffrn_reflns_Laue_measured_fraction_max 0.9972
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            65892
_diffrn_reflns_point_group_measured_fraction_full 1.0000
_diffrn_reflns_point_group_measured_fraction_max 0.9972
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         79.95
_diffrn_reflns_theta_min         4.28
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.973
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.943
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.118a (Rigaku Oxford Diffraction, 2025)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.339
_exptl_crystal_description       block
_exptl_crystal_F_000             1168.648
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.3744
_refine_diff_density_min         -0.3339
_refine_diff_density_rms         0.0360
_refine_ls_d_res_high            0.7829
_refine_ls_d_res_low             10.3345
_refine_ls_extinction_coef       0.00056(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.0428
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     632
_refine_ls_number_reflns         6023
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0428
_refine_ls_R_factor_all          0.0252
_refine_ls_R_factor_gt           0.0222
_refine_ls_shift/su_max          0.0004
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0279P)^2^+0.5564P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0556
_refine_ls_wR_factor_ref         0.0571
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              12
_reflns_limit_h_min              -15
_reflns_limit_k_max              15
_reflns_limit_k_min              0
_reflns_limit_l_max              23
_reflns_limit_l_min              -11
_reflns_number_gt                5517
_reflns_number_total             6023
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d6cc00297h2.cif
_cod_data_source_block           IL190925V2
_cod_depositor_comments          'Adding full bibliography for 7135369.cif.'
_cod_database_code               7135369
_chemical_oxdiff_formula         'C31 H34 N2 O2 S Ni '
_diffrn_oxdiff_digest_hkl
;
435239e22ab8112f572eab254a5b8ad4efa233
;
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name IL190925V2.par
_olex2_refinement_description
;
;
_olex2_refine_details
;
Refinement using NoSpherA2, an implementation of
NOn-SPHERical Atom-form-factors in Olex2.
Please cite:
F. Kleemiss et al. Chem. Sci. DOI 10.1039/D0SC05526C - 2021
NoSpherA2 implementation of HAR makes use of
tailor-made aspherical atomic form factors calculated
on-the-fly from a Hirshfeld-partitioned electron density (ED) - not from
spherical-atom form factors.

The ED is calculated from a gaussian basis set single determinant SCF
wavefunction - either Hartree-Fock or DFT using selected funtionals
- for a fragment of the crystal.
This fragment can be embedded in an electrostatic crystal field by employing cluster charges
or modelled using implicit solvation models, depending on the software used.
The following options were used:
   SOFTWARE:       ORCA 5.0
   PARTITIONING:   NoSpherA2
   INT ACCURACY:   Normal
   METHOD:         M062X
   BASIS SET:      def2-SVP
   CHARGE:         0
   MULTIPLICITY:   1
   DATE:           2025-09-24_09-36-37
;
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 5.573
_oxdiff_exptl_absorpt_empirical_full_min 0.332