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_4517528
_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         'C39 H61 N Ni P2, C3 H3'
_chemical_formula_sum            'C42 H64 N Ni P2'
_chemical_formula_weight         703.59
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-11-19
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_cell_angle_alpha                90
_cell_angle_beta                 105.834(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.8848(3)
_cell_length_b                   19.0951(4)
_cell_length_c                   17.6180(4)
_cell_measurement_reflns_used    7158
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      78.5510
_cell_measurement_theta_min      3.8550
_cell_volume                     3846.55(16)
_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 1.000
_diffrn_measured_fraction_theta_max 0.961
_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     -9.00  27.00   0.50   15.00    --  -49.37  19.00  60.00   72
  2  \w     -9.00  27.00   0.50   15.00    --  -49.37  19.00 120.00   72
  3  \w     -9.00  27.00   0.50   15.00    --  -49.37  19.00 150.00   72
  4  \w     -9.00  27.00   0.50   15.00    --  -49.37  19.00 -90.00   72
  5  \w    -38.00   6.00   0.50   30.00    --  -70.00  38.00 -90.00   88
  6  \w    -68.00   2.00   0.50   30.00    --  -70.00  57.00-120.00  140
  7  \w     59.00 120.00   0.50   15.00    --   48.87 178.00-180.00  122
  8  \w   -120.00 -38.00   0.50   15.00    --  -49.37-178.00  60.00  164
  9  \w   -145.00 -56.00   0.50   30.00    --  -70.00 -38.00 120.00  178
 10  \w     38.00  68.00   0.50   30.00    --  110.00 -57.00 150.00   60
 11  \w     40.00 103.00   0.50   30.00    --  110.00-125.00 150.00  126
 12  \w     38.00  64.00   0.50   30.00    --  110.00 -57.00  30.00   52
 13  \w     40.00  89.00   0.50   30.00    --  110.00 -99.00 -30.00   98
 14  \w     46.00 102.00   0.50   30.00    --  110.00 -99.00 -90.00  112
 15  \w     46.00 117.00   0.50   30.00    --  110.00-125.00-150.00  142
 16  \w     38.00  68.00   0.50   30.00    --  110.00 -57.00-120.00   60
 17  \w     40.00  66.00   0.50   30.00    --  110.00 -57.00 -60.00   52
 18  \w    118.00 176.00   0.50   30.00    --  110.00  19.00-120.00  116
 19  \w    132.00 169.00   0.50   30.00    --  110.00  77.00-150.00   74
 20  \w     99.00 177.00   0.50   30.00    --  110.00  38.00-180.00  156
 21  \w     88.00 114.00   0.50   30.00    --  110.00  77.00-150.00   52
 22  \w    127.00 177.00   0.50   30.00    --  110.00  38.00  30.00  100
 23  \w     40.00  92.00   0.50   30.00    --  110.00-125.00  90.00  104
;
_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      -0.0036590000
_diffrn_orient_matrix_UB_12      0.0805189000
_diffrn_orient_matrix_UB_13      -0.0063527000
_diffrn_orient_matrix_UB_21      -0.1346978000
_diffrn_orient_matrix_UB_22      -0.0022234000
_diffrn_orient_matrix_UB_23      -0.0246662000
_diffrn_orient_matrix_UB_31      0.0002234000
_diffrn_orient_matrix_UB_32      0.0052394000
_diffrn_orient_matrix_UB_33      0.0872463000
_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  0.0948
_diffrn_reflns_av_unetI/netI     0.0765
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            32151
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.977
_diffrn_reflns_theta_min         3.487
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.717
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.800
_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 dark orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.215
_exptl_crystal_description       needle
_exptl_crystal_F_000             1524
_exptl_crystal_size_max          0.169
_exptl_crystal_size_mid          0.022
_exptl_crystal_size_min          0.019
_refine_diff_density_max         1.294
_refine_diff_density_min         -0.594
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     444
_refine_ls_number_reflns         8081
_refine_ls_number_restraints     159
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0977
_refine_ls_R_factor_gt           0.0689
_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^)+(0.1182P)^2^+0.4663P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1747
_refine_ls_wR_factor_ref         0.1930
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5751
_reflns_number_total             8081
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c00393_si_007.cif
_cod_data_source_block           bm241019_1_1
_cod_depositor_comments
'Adding full bibliography for 4517528--4517534.cif.'
_cod_original_cell_volume        3846.54(16)
_cod_database_code               4517528
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C45H67NNiP2
_reflns_odcompleteness_completeness 99.99
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C2A-C1A \\sim C2B-C1B \\sim C3B-C2B \\sim C3A_$1-C1A \\sim C3B_$1-C1B \\sim
C3A-C2A \\sim C3B-C1B_$1
 \\sim C3A_$1-C2A_$1 \\sim C2B_$1-C1B_$1 \\sim C3A-C1A_$1 \\sim C3B_$1-C2B_$1
\\sim C2A_$1-C1A_$1
 with sigma of 0.02
3. Restrained planarity
 C1A_$1, C1A, C2A, C3A_$1, C3A, C2A_$1
 with sigma of 0.1
 C1B_$1, C3B, C2B, C1B, C2B_$1, C3B_$1
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C3B \\sim C2B \\sim C1B: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C3A \\sim C1A \\sim C2A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 C3B, C2B, C1B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C3A, C1A, C2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N1, C2, C3, C4, C6, C7, C5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C3B)=Sof(H3B)=Sof(C2B)=Sof(H2B)=Sof(C1B)=Sof(H1BA)=1-FVAR(1)
 Sof(C1A)=Sof(H1AA)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C16(H16), C22(H22), C28(H28), C34(H34)
7.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B),
 C20(H20A,H20B), C21(H21A,H21B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B),
  C26(H26A,H26B), C27(H27A,H27B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,
 H31B), C32(H32A,H32B), C33(H33A,H33B), C35(H35A,H35B), C36(H36A,H36B),
 C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B)
7.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15), C1A(H1AA), C2A(H2A), C3A(H3A), C3B(H3B), C2B(H2B),
 C1B(H1BA)
7.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_shelx_res_checksum              89556
_shelx_hkl_checksum              62900
_olex2_date_sample_data_collection 2019-10-24
_olex2_date_sample_submission    2019-10-24
_olex2_submission_original_sample_id bm241019_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 3.464
_oxdiff_exptl_absorpt_empirical_full_min 0.500