When Weaker Can Be Tougher: The Role of Oxidation State (I) in P- vs N-Ligand-Derived Ni-Catalyzed Trifluoromethylthiolation of Aryl Halides.
Kalvet, Indrek; Guo, Qianqian; Tizzard, Graham J.; Schoenebeck, Franziska; ACS catalysis 7 (2017) 2126–2132; doi:10.1021/acscatal.6b03344

data_4514061
_publ_section_title
;
 When Weaker Can Be Tougher: The Role of Oxidation State (I) in P- vs
 N-Ligand-Derived Ni-Catalyzed Trifluoromethylthiolation of Aryl Halides.
;
_journal_issue                   3
_journal_name_full               'ACS catalysis'
_journal_page_first              2126
_journal_page_last               2132
_journal_paper_doi               10.1021/acscatal.6b03344
_journal_volume                  7
_journal_year                    2017
_chemical_formula_moiety         'C68 H56 Fe2 I2 Ni2 P4, C4 H8 O'
_chemical_formula_sum            'C72 H64 Fe2 I2 Ni2 O P4'
_chemical_formula_weight         1552.03
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-02-10
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2016.01.25 svn.r3250 for OlexSys, GUI svn.r5148)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.394(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.6771(5)
_cell_length_b                   13.9547(3)
_cell_length_c                   19.1841(4)
_cell_measurement_reflns_used    20328
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.4680
_cell_measurement_theta_min      1.9890
_cell_volume                     6338.4(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrystalClear-SM Expert 3.1 b27 (Rigaku, 2013)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku HG Saturn724+ (2x2 bin mode)'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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   -106.00  74.00   1.00   20.00    --  -16.00   0.00-150.00  180
  2  \w    -88.00  20.00   1.00   20.00    --  -16.00 -54.00-180.00  108
  3  \w    -55.00  12.00   1.00   20.00    --  -16.00  72.00-120.00   67
  4  \w    -43.00  74.00   1.00   20.00    --  -16.00  72.00 -60.00  117
  5  \w    -30.00 -15.00   1.00   20.00    --  -16.00 -72.00-120.00   15
  6  \w    -68.00   0.00   1.00   20.00    --  -16.00   0.00  30.00   68
;
_diffrn_measurement_device       'four-circle \k goniometer'
_diffrn_measurement_device_type
'Rigaku FRE+ equipped with HF Varimax confocal mirrors and an AFC12 goniometer and HG Saturn 724+ detector'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroLoop'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0294565000
_diffrn_orient_matrix_UB_12      -0.0092328000
_diffrn_orient_matrix_UB_13      -0.0001439000
_diffrn_orient_matrix_UB_21      -0.0007795000
_diffrn_orient_matrix_UB_22      -0.0040101000
_diffrn_orient_matrix_UB_23      -0.0368414000
_diffrn_orient_matrix_UB_31      0.0054059000
_diffrn_orient_matrix_UB_32      0.0498277000
_diffrn_orient_matrix_UB_33      -0.0030742000
_diffrn_radiation_collimation    0.2
_diffrn_radiation_monochromator  'Confocal mirrors, HF Varimax'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0599
_diffrn_reflns_av_unetI/netI     0.0486
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            41356
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        27.483
_diffrn_reflns_theta_max         27.483
_diffrn_reflns_theta_min         2.123
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           55.0
_diffrn_source_power             2.475
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku FRE+'
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    2.153
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92789
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.626
_exptl_crystal_description       block
_exptl_crystal_F_000             3112
_exptl_crystal_recrystallization_method
'The material was recrystallised from THF by vapour diffusion with hexane'
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.098
_refine_diff_density_min         -0.435
_refine_diff_density_rms         0.112
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     397
_refine_ls_number_reflns         7243
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0609
_refine_ls_R_factor_gt           0.0395
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0346P)^2^+12.7976P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0735
_refine_ls_wR_factor_ref         0.0798
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5648
_reflns_number_total             7243
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs6b03344_si_004.cif
_cod_data_source_block           2016gjt0002za
_cod_depositor_comments
'Adding full bibliography for 4514030--4514061.cif.'
_cod_database_code               4514061
_chemical_oxdiff_formula         'C34 H28 Fe I Ni P2'
_reflns_odcompleteness_completeness 99.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
3. Uiso/Uaniso restraints and constraints
: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 O101_1, C101_1, C102_1, C104_1, C103_1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: O101(0.5) C104(0.5) H10A(0.5) H10B(0.5) C103(0.5) H10C(0.5)
 H10D(0.5) C102(0.5) H10E(0.5) H10F(0.5) C101(0.5) H10G(0.5) H10H(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C104(H10A,H10B), C103(H10C,H10D), C102(H10E,H10F), C101(H10G,H10H)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C10(H10), C12(H12),
 C13(H13), C14(H14), C15(H15), C16(H16), C18(H18), C19(H19), C20(H20), C21(H21),
  C22(H22), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28), C30(H30),
 C31(H31), C32(H32), C33(H33), C34(H34)
;
_shelx_res_checksum              85345
_shelx_hkl_checksum              70264
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-02-08
_olex2_date_sample_submission    2016-02-03
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_original_sample_id IK_N643(THF/Hex)
_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 1.245
_oxdiff_exptl_absorpt_empirical_full_min 0.899