Elucidating the Mechanism of Aryl Aminations Mediated by NHC-Supported Nickel Complexes: Evidence for a Nonradical Ni(0)/Ni(II) Pathway
Rull, Silvia G.; Funes-Ardoiz, Ignacio; Maya, Celia; Maseras, Feliu; Fructos, Manuel R.; Belderrain, Tomás R.; Nicasio, M. Carmen; ACS Catalysis 8 (2018) 3733–; doi:10.1021/acscatal.8b00856

data_4515602
_publ_section_title
;
 Elucidating the Mechanism of Aryl Aminations Mediated by NHC-Supported
 Nickel Complexes: Evidence for a Nonradical Ni(0)/Ni(II) Pathway
;
_journal_issue                   5
_journal_name_full               'ACS Catalysis'
_journal_page_first              3733
_journal_paper_doi               10.1021/acscatal.8b00856
_journal_volume                  8
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C44 H54 N4 Ni'
_chemical_formula_sum            'C44 H54 N4 Ni'
_chemical_formula_weight         697.62
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_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'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-02-25
_audit_creation_method
;

Olex2 1.2

(compiled 2017.02.23 svn.r3390 for OlexSys, GUI svn.r5320)

;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.1006(7)
_cell_length_b                   18.0014(13)
_cell_length_c                   42.163(3)
_cell_measurement_reflns_used    9192
_cell_measurement_temperature    100
_cell_measurement_theta_max      26.02
_cell_measurement_theta_min      2.31
_cell_volume                     7666.3(9)
_computing_cell_refinement       'SAINT v8.35A (Bruker, 2016)'
_computing_data_collection       'Bruker Apex3, 2016'
_computing_data_reduction        'SAINT v8.35A (Bruker, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2014)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'Fixed Chi Bruker diffractometer'
_diffrn_measurement_device_type  'BRUKER D8 FIXED-CHI'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  multilayer
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0743
_diffrn_reflns_av_unetI/netI     0.0792
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       52
_diffrn_reflns_limit_l_min       -52
_diffrn_reflns_number            58853
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.054
_diffrn_reflns_theta_min         2.236
_diffrn_source                   'microfocus sealed x-ray tube'
_diffrn_source_type              'Incoatec I/mS high brilliance'
_diffrn_standards_decay_%        0
_exptl_absorpt_coefficient_mu    0.541
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.5831
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;

SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. 

wR2(int) was 0.1032 before and 0.0756 after correction. 

The Ratio of minimum to maximum transmission is 0.7824. 

The \l/2 correction factor is Not present.

;
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.209
_exptl_crystal_description       block
_exptl_crystal_F_000             2992
_exptl_crystal_recrystallization_method
'The material was recrystallised from toluene by slow cooling'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.055
_refine_diff_density_max         0.424
_refine_diff_density_min         -0.355
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details
;

 Flack x determined using 4469 quotients [(I+)-(I-)]/[(I+)+(I-)]

 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).

;
_refine_ls_abs_structure_Flack   -0.001(7)
_refine_ls_extinction_coef       0.00120(16)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     906
_refine_ls_number_reflns         15127
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0689
_refine_ls_R_factor_gt           0.0487
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0332P)^2^+3.1768P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0911
_refine_ls_wR_factor_ref         0.0976
_reflns_Friedel_coverage         0.806
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                12344
_reflns_number_total             15127
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b00856_si_004.cif
_cod_data_source_block           Compound_4
_cod_original_cell_volume        7666.2(9)
_cod_database_code               4515602
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;

1. Fixed Uiso

 At 1.2 times of:

  All C(H) groups

 At 1.5 times of:

  All C(H,H,H) groups

2.a Ternary CH refined with riding coordinates:

 C10A(H10A), C13A(H13A), C22A(H22A), C25A(H25A), C10B(H10B), C13B(H13B),

 C22B(H22B), C25B(H25B)

2.b Aromatic/amide H refined with riding coordinates:

 C2A(H2A), C3A(H3A), C6A(H6A), C7A(H7A), C8A(H8A), C18A(H18A), C19A(H19A),

 C20A(H20A), C29A(H29A), C30A(H30A), C31A(H31A), C37A(H37A), C38A(H38A),

 C40A(H40A), C41A(H41A), C42A(H42A), C43A(H43A), C2B(H2B), C3B(H3B), C6B(H6B),

 C7B(H7B), C8B(H8B), C18B(H18B), C19B(H19B), C20B(H20B), C29B(H29B), C30B(H30B),

  C31B(H31B), C37B(H37B), C38B(H38B), C40B(H40B), C41B(H41B), C42B(H42B),

 C43B(H43B)

2.c Idealised Me refined as rotating group:

 C11A(H11A,H11B,H11C), C12A(H12A,H12B,H12C), C14A(H14A,H14B,H14C), C15A(H15A,

 H15B,H15C), C23A(H23A,H23B,H23C), C24A(H24A,H24B,H24C), C26A(H26A,H26B,H26C),

 C27A(H27A,H27B,H27C), C34A(H34A,H34B,H34C), C35A(H35A,H35B,H35C), C36A(H36A,

 H36B,H36C), C11B(H11D,H11E,H11F), C12B(H12D,H12E,H12F), C14B(H14D,H14E,H14F),

 C15B(H15D,H15E,H15F), C23B(H23D,H23E,H23F), C24B(H24D,H24E,H24F), C26B(H26D,

 H26E,H26F), C27B(H27D,H27E,H27F), C34B(H34D,H34E,H34F), C35B(H35D,H35E,H35F),

 C36B(H36D,H36E,H36F)

;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a 100 micro/m MITIGEN holder in perfluoroether oil'
_olex2_submission_special_instructions 'No special instructions were received'