Catalytic C-F bond activation of geminal difluorocyclopropanes by nickel(I) complexes via a radical mechanism
Jan Wenz; Christoph A. Rettenmeier; Hubert Wadepohl; Lutz H. Gade; Chem.Commun. 52 (2016) 202–; doi:10.1039/c5cc08950F

data_7118173
_publ_section_title
;
 Catalytic C-F bond activation of geminal difluorocyclopropanes by
 nickel(I) complexes via a radical mechanism
;
_journal_name_full               Chem.Commun.
_journal_page_first              202
_journal_paper_doi               10.1039/c5cc08950F
_journal_volume                  52
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C24 H23 F2 N3 Ni O2'
_chemical_formula_sum            'C24 H23 F2 N3 Ni O2'
_chemical_formula_weight         482.16
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      19
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_cr31
_audit_creation_date             2015-09-24
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3151 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-09-25 deposited with the CCDC.
2015-11-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.148(5)
_cell_length_b                   11.913(5)
_cell_length_c                   17.409(8)
_cell_measurement_reflns_used    8050
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      32.11
_cell_measurement_theta_min      2.32
_cell_volume                     2104.6(17)
_computing_cell_refinement
;
SAINT (see _computing_data_reduction). Includes estimated systematic errors
 of the unit cell constants from Monte Carlo simulations.
;
_computing_data_collection       'SMART-5.631 (Bruker AXS, 2003)'
_computing_data_reduction
'SAINT V8.18C (Bruker AXS, 1997-2013),SADABS-2009_1 (Sheldrick and Bruker AXS, 1997-2014)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material
'encif (Wadepohl, 2009-14); encifer 1.5 (CCDC, 2014)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_environment      'perfluoro polyether oil / N~2~'
_diffrn_ambient_temperature      100(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.19
_diffrn_detector_type            CCD-PXL-KAF2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker AXS Smart 1000'
_diffrn_measurement_method       '\f- and \w-scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0432
_diffrn_reflns_av_unetI/netI     0.0296
_diffrn_reflns_laue_measured_fraction_full 1.000
_diffrn_reflns_laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            52838
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.475
_diffrn_reflns_theta_min         2.071
_diffrn_source                   'sealed X-Ray tube (Mo)'
_diffrn_source_type              'fine focus tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.967
_exptl_absorpt_correction_T_max  0.7464
_exptl_absorpt_correction_T_min  0.6799
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
multi-scan from symmetry-related measurements (Blessing 1995)
SADABS (see _computing_data_reduction)
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.522
_exptl_crystal_density_meas      .
_exptl_crystal_description       plate
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.160
_exptl_crystal_size_mid          0.140
_exptl_crystal_size_min          0.050
_refine_diff_density_max         0.559
_refine_diff_density_min         -0.321
_refine_diff_density_rms         0.070
_refine_ls_abs_structure_details
;
 Flack x determined using 2692 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.006(4)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     293
_refine_ls_number_reflns         7254
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0366
_refine_ls_R_factor_gt           0.0305
_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^)+(0.0354P)^2^+0.6205P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0681
_refine_ls_wR_factor_ref         0.0710
_reflns_Friedel_coverage         0.763
_reflns_friedel_fraction_full    1.000
_reflns_friedel_fraction_max     0.933
_reflns_number_gt                6656
_reflns_number_total             7254
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc08950f2.cif
_cod_data_source_block           ga_cr31
_cod_database_code               7118173
_audit_block_refno               1576
_audit_block_usercomment         cr606
_shelx_estimated_absorpt_t_max   0.953
_shelx_estimated_absorpt_t_min   0.861
_shelxl_version_number           2014/7
_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:
 C1(H1A), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C6(H6A,H6B), C7(H7A,H7B), C11(H11A,H11B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C9(H9), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C20(H20),
 C21(H21), C22(H22), C23(H23), C24(H24)
;
_shelx_res_checksum              4149
_olex2_submission_special_instructions 'No special instructions were received'