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_4514031
_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         'C34 H28 Fe I2 Ni P2, C6 H6'
_chemical_formula_sum            'C40 H34 Fe I2 Ni P2'
_chemical_formula_weight         944.97
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-02-17
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2016.02.16 svn.r3264 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                91.917(3)
_cell_angle_beta                 99.127(4)
_cell_angle_gamma                94.971(2)
_cell_formula_units_Z            2
_cell_length_a                   8.9532(2)
_cell_length_b                   10.0303(3)
_cell_length_c                   20.4331(11)
_cell_measurement_reflns_used    7658
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.5390
_cell_measurement_theta_min      2.0610
_cell_volume                     1802.83(12)
_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 0.999
_diffrn_measured_fraction_theta_max 0.990
_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    7.00    --  -16.00   0.00 -60.00  180
  2  \w    -69.00  23.00   1.00    7.00    --  -16.00 -72.00  60.00   92
  3  \w    -54.00  23.00   1.00    7.00    --  -16.00 -72.00-120.00   77
  4  \w    -28.00  74.00   1.00    7.00    --  -16.00  72.00-180.00  102
  5  \w    -25.00  -1.00   1.00    7.00    --  -16.00  54.00   0.00   24
  6  \w    -32.00  46.00   1.00    7.00    --  -16.00  72.00 -60.00   78
;
_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      0.0036738000
_diffrn_orient_matrix_UB_12      -0.0058659000
_diffrn_orient_matrix_UB_13      0.0347039000
_diffrn_orient_matrix_UB_21      0.0107700000
_diffrn_orient_matrix_UB_22      0.0707743000
_diffrn_orient_matrix_UB_23      0.0047015000
_diffrn_orient_matrix_UB_31      -0.0797818000
_diffrn_orient_matrix_UB_32      0.0025944000
_diffrn_orient_matrix_UB_33      -0.0035349000
_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     0.71073
_diffrn_reflns_av_unetI/netI     0.0257
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            9996
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         2.314
_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    2.754
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.95223
_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    1.741
_exptl_crystal_description       block
_exptl_crystal_F_000             928
_exptl_crystal_recrystallization_method
'The material was recrystallised from benzene by vapour diffusion with hexane'
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         3.023
_refine_diff_density_min         -0.982
_refine_diff_density_rms         0.145
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     416
_refine_ls_number_reflns         9996
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0454
_refine_ls_R_factor_gt           0.0415
_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^)+(0.0230P)^2^+11.9220P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0863
_refine_ls_wR_factor_ref         0.0878
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9386
_reflns_number_total             9996
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs6b03344_si_006.cif
_cod_data_source_block           2016gjt0006z_twin1_hklf4
_cod_depositor_comments
;Adding full bibliography for 4514030--4514031.cif.

 Adding full bibliography for 4514030--4514061.cif.
;
_cod_database_code               4514031
_chemical_oxdiff_formula         'C34 H28 P2 Fe1 Ni1 I1'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5404(7) 0.4596(7)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3.a 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), C101(H101), C102(H102), C103(H103),
 C104(H104), C105(H105), C106(H106)
;
_shelx_res_checksum              31028
_shelx_hkl_checksum              20710
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-02-10
_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(Bz/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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.259
_oxdiff_exptl_absorpt_empirical_full_min 0.861
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
_twin_special_details
;
Component 2 rotated by 179.9936\% 
 around [0.00 0.00 1.00] (reciprocal) or [0.35 0.09 0.93] (direct)
;