Nickel-Catalyzed Amination of Aryl Thioethers: A Combined Synthetic and Mechanistic Study
Bismuto, Alessandro; Delcaillau, Tristan; Müller, Patrick; Morandi, Bill; ACS Catalysis  (2020) 4630–4639; doi:10.1021/acscatal.0c00393

data_4517530
_publ_section_title
;
 Nickel-Catalyzed Amination of Aryl Thioethers: A Combined Synthetic and
 Mechanistic Study
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              4630
_journal_page_last               4639
_journal_paper_doi               10.1021/acscatal.0c00393
_journal_year                    2020
_chemical_formula_moiety         'C52 H96 Ni P4'
_chemical_formula_sum            'C52 H96 Ni P4'
_chemical_formula_weight         903.87
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-10-03
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_cell_angle_alpha                73.619(2)
_cell_angle_beta                 89.5920(10)
_cell_angle_gamma                75.811(2)
_cell_formula_units_Z            2
_cell_length_a                   12.7568(2)
_cell_length_b                   12.7744(2)
_cell_length_c                   17.1688(3)
_cell_measurement_reflns_used    25868
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.0280
_cell_measurement_theta_min      2.6690
_cell_volume                     2596.58(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.42a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.42a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.42a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 300K'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.968
_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    -59.00 -30.00   0.50    1.07    --   14.00 164.00 -19.37   58
  2  \w     -9.00  37.00   0.50    1.07    --   22.00  94.00-126.72   92
  3  \w     20.00  46.00   0.50    1.07    --   50.00  90.00-173.41   52
  4  \w     37.00  63.00   0.50    1.07    --   62.00  81.00-166.02   52
  5  \w     51.00  77.00   0.50    1.07    --   74.00  77.00-134.53   52
  6  \w     68.00 142.00   0.50    3.50    --   86.00  62.00-140.80  148
  7  \w    127.00 173.00   0.50    3.50    --  110.00  77.00-120.00   92
  8  \w    146.00 172.00   0.50    3.50    --  110.00  77.00 -60.00   52
  9  \w    133.00 164.00   0.50    3.50    --  110.00  77.00   0.00   62
 10  \w    135.00 167.00   0.50    3.50    --  110.00  57.00 -60.00   64
 11  \w    136.00 175.00   0.50    3.50    --  110.00  77.00  30.00   78
 12  \w    108.00 161.00   0.50    3.50    --   90.00  61.00 -54.32  106
 13  \w     93.00 126.00   0.50    1.07    --   74.00  73.00 -59.41   66
 14  \w     87.00 114.00   0.50    3.50    --  110.00  77.00-120.00   54
 15  \w     96.00 172.00   0.50    3.50    --  110.00  57.00 -90.00  152
 16  \w     99.00 126.00   0.50    1.07    --   78.00  76.00-160.72   54
 17  \w    100.00 143.00   0.50    3.50    --  110.00  38.00-180.00   86
 18  \w     86.00 168.00   0.50    3.50    --  110.00  77.00-150.00  164
 19  \w     87.00 114.00   0.50    3.50    --  110.00  77.00   0.00   54
 20  \w    102.00 148.00   0.50    3.50    --  110.00  48.00  53.09   92
 21  \w     95.00 124.00   0.50    1.07    --   58.00  81.00 142.15   58
 22  \w     86.00 175.00   0.50    3.50    --  110.00  77.00 120.00  178
 23  \w    140.00 178.00   0.50    3.50    --  110.00  57.00 150.00   76
 24  \w     97.00 163.00   0.50    3.50    --  110.00  48.00  15.54  132
 25  \w     94.00 120.00   0.50    3.50    --  110.00  57.00 -60.00   52
 26  \w     94.00 137.00   0.50    3.50    --  110.00  57.00-120.00   86
 27  \w     94.00 174.00   0.50    3.50    --  110.00  57.00-180.00  160
 28  \w     86.00 113.00   0.50    3.50    --  110.00  77.00 -60.00   54
 29  \w     86.00 174.00   0.50    3.50    --  110.00  77.00 -30.00  176
 30  \w     95.00 131.00   0.50    3.50    --  110.00  57.00 120.00   72
 31  \w     89.00 175.00   0.50    3.50    --  110.00  77.00  90.00  172
 32  \w     94.00 134.00   0.50    3.50    --  110.00  57.00 150.00   80
 33  \w     86.00 176.00   0.50    3.50    --  110.00  77.00  60.00  180
 34  \w     87.00 112.00   0.50    3.50    --  110.00  77.00  30.00   50
 35  \w     74.00  99.00   0.50    3.50    --   90.00  61.00 -54.32   50
 36  \w     60.00 104.00   0.50    1.07    --   78.00  65.00 -10.22   88
 37  \w     52.00  85.00   0.50    1.07    --   74.00  73.00 -59.41   66
 38  \w     29.00  56.00   0.50    1.07    --   54.00  80.00  54.16   54
 39  \w     37.00  63.00   0.50    1.07    --   58.00  75.00  68.13   52
 40  \w     51.00  82.00   0.50    1.07    --   74.00  76.00 105.10   62
 41  \w     66.00 153.00   0.50    3.50    --   82.00  59.00  96.36  174
 42  \w     52.00  87.00   0.50    1.07    --   74.00  76.00 153.77   70
 43  \w     34.00  59.00   0.50    1.07    --   58.00  81.00 142.15   50
 44  \w     26.00  51.00   0.50    1.07    --   48.87  77.00 150.00   50
 45  \w     48.00  74.00   0.50    1.07    --   74.00  82.00  56.69   52
 46  \w     55.00  86.00   0.50    1.07    --   78.00  75.00  51.31   62
 47  \w     29.00  81.00   0.50    1.07    --   54.00  81.00 -46.02  104
 48  \w     34.00  59.00   0.50    1.07    --   58.00  81.00  -2.97   50
 49  \w     36.00  62.00   0.50    1.07    --   62.00  82.00-105.19   52
 50  \w     55.00  81.00   0.50    1.07    --   78.00  76.00-160.72   52
 51  \w     -1.00  24.00   0.50    1.07    --   30.00  96.00-160.18   50
 52  \w    -59.00  32.00   0.50    1.07    --  -26.00  96.00-154.22  182
 53  \w    -36.00   1.00   0.50    3.50    --  -70.00  38.00 -90.00   74
 54  \w    -72.00 -46.00   0.50    3.50    --  -70.00 -77.00  30.00   52
 55  \w    -74.00 -47.00   0.50    3.50    --  -70.00 -74.00  86.63   54
 56  \w    -75.00 -48.00   0.50    3.50    --  -70.00 -77.00 150.00   54
 57  \w    -68.00 -43.00   0.50    3.50    --  -70.00 -83.00 132.07   50
 58  \w    -82.00 -26.00   0.50    1.07    --  -49.37 -77.00 120.00  112
 59  \w    -72.00 -46.00   0.50    3.50    --  -70.00 -77.00   0.00   52
 60  \w    -79.00 -46.00   0.50    3.50    --  -70.00 -77.00 -60.00   66
 61  \w    -73.00 -47.00   0.50    3.50    --  -70.00 -76.00-105.31   52
 62  \w    -79.00 -47.00   0.50    3.50    --  -70.00 -77.00-180.00   64
 63  \w   -100.00 -48.00   0.50    3.50    --  -70.00 -78.00-125.78  104
 64  \w    -72.00 -45.00   0.50    3.50    --  -70.00 -79.00 -17.38   54
 65  \w   -105.00 -49.00   0.50    1.07    --  -49.37 -57.00  30.00  112
 66  \w    -98.00 -36.00   0.50    1.07    --  -49.37 -19.00 150.00  124
 67  \w    -64.00  18.00   0.50    1.07    --  -49.37  57.00 150.00  164
 68  \w    -25.00   9.00   0.50    1.07    --   48.87 -19.00 -30.00   68
 69  \w     67.00  94.00   0.50    3.50    --  110.00 -99.00 -60.00   54
 70  \w     95.00 122.00   0.50    3.50    --  110.00 -77.00   0.00   54
 71  \w     75.00 102.00   0.50    3.50    --  110.00 -99.00  60.00   54
 72  \w     62.00 116.00   0.50    3.50    --  110.00-125.00  30.00  108
 73  \w     46.00  80.00   0.50    3.50    --  110.00 -77.00   0.00   68
 74  \w     44.00  72.00   0.50    3.50    --  110.00 -99.00  60.00   56
 75  \w     46.00 112.00   0.50    3.50    --  110.00-116.00 109.00  132
 76  \w     41.00  87.00   0.50    3.50    --  110.00 -99.00 150.00   92
 77  \w     42.00  96.00   0.50    3.50    --  110.00 -99.00-120.00  108
 78  \w     85.00 134.00   0.50    3.50    --  110.00 -77.00-180.00   98
 79  \w     40.00 110.00   0.50    3.50    --  110.00 -99.00-180.00  140
 80  \w     47.00  72.00   0.50    3.50    --  110.00 -77.00-180.00   50
 81  \w    -91.00 -27.00   0.50    3.50    --  -70.00 125.00 -30.00  128
 82  \w   -130.00-104.00   0.50    3.50    --  -70.00 -77.00 150.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 300K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0108359000
_diffrn_orient_matrix_UB_12      -0.0810366000
_diffrn_orient_matrix_UB_13      0.0834271000
_diffrn_orient_matrix_UB_21      0.0075793000
_diffrn_orient_matrix_UB_22      -0.0955921000
_diffrn_orient_matrix_UB_23      -0.0396316000
_diffrn_orient_matrix_UB_31      0.1241402000
_diffrn_orient_matrix_UB_32      -0.0343525000
_diffrn_orient_matrix_UB_33      0.0159869000
_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  0.0669
_diffrn_reflns_av_unetI/netI     0.0360
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            64455
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.901
_diffrn_reflns_theta_min         2.689
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.927
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.696
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.42a (Rigaku Oxford Diffraction, 2019)
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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.156
_exptl_crystal_description       block
_exptl_crystal_F_000             992
_exptl_crystal_size_max          0.148
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.096
_refine_diff_density_max         1.455
_refine_diff_density_min         -0.858
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     514
_refine_ls_number_reflns         10960
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0728
_refine_ls_R_factor_gt           0.0655
_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^)+(0.1247P)^2^+1.7673P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1774
_refine_ls_wR_factor_ref         0.1854
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9408
_reflns_number_total             10960
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c00393_si_002.cif
_cod_data_source_block           bm031019_1_1
_cod_depositor_comments
'Adding full bibliography for 4517528--4517534.cif.'
_cod_original_cell_volume        2596.59(8)
_cod_database_code               4517530
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C52H96NiP4
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C5(H5), C11(H11), C17(H17), C23(H23), C29(H29), C35(H35), C41(H41), C47(H47)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C6(H6A,H6B), C7(H7A,H7B),
 C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C12(H12A,H12B), C13(H13A,H13B),
 C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C18(H18A,H18B), C19(H19A,H19B),
  C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C24(H24A,H24B), C25(H25A,
 H25B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C30(H30A,H30B),
 C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B), C34(H34A,H34B), C36(H36A,H36B),
  C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B), C42(H42A,
 H42B), C43(H43A,H43B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B),
 C48(H48A,H48B), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B), C52(H52A,H52B)
;
_shelx_res_checksum              40412
_shelx_hkl_checksum              84342
_olex2_date_sample_data_collection 2019-10-02
_olex2_date_sample_submission    2019-10-02
_olex2_submission_original_sample_id bm031019_1_1
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.046
_oxdiff_exptl_absorpt_empirical_full_min 0.468