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_4515603
_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_formula_moiety         'C96 H120 Cl3 N9 Ni3, 2(C7 H8)'
_chemical_formula_sum            'C110 H136 Cl3 N9 Ni3'
_chemical_formula_weight         1866.75
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_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
_audit_creation_date             2017-10-23
_audit_creation_method
;

Olex2 1.2

(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)

;
_cell_angle_alpha                90
_cell_angle_beta                 90.462(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.6781(11)
_cell_length_b                   16.5463(7)
_cell_length_c                   22.7174(9)
_cell_measurement_reflns_used    9356
_cell_measurement_temperature    100
_cell_measurement_theta_max      26.05
_cell_measurement_theta_min      2.46
_cell_volume                     10027.7(7)
_computing_cell_refinement       'Bruker Apex3, 2017'
_computing_data_collection       'Bruker Apex3, 2017'
_computing_data_reduction        'SAINT v8.38A (Bruker, 2017)'
_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
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'Bruker D8 Quest'
_diffrn_measurement_device_type  'Bruker CHi Fixed D8 Quest'
_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  0.0883
_diffrn_reflns_av_unetI/netI     0.0410
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            160433
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.350
_diffrn_reflns_theta_min         2.151
_diffrn_source                   'microfocus sealed x-ray tube'
_diffrn_source_type              'Incoatec I/mS high brilliance'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.689
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.6259
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;

SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. 

wR2(int) was 0.1245 before and 0.0734 after correction. 

The Ratio of minimum to maximum transmission is 0.8398. 

The \l/2 correction factor is Not present.

;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.237
_exptl_crystal_description       prism
_exptl_crystal_F_000             3976
_exptl_crystal_recrystallization_method
'Crystallised from toluene by slow evaporation'
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.502
_refine_diff_density_min         -0.459
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1216
_refine_ls_number_reflns         18345
_refine_ls_number_restraints     291
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0749
_refine_ls_R_factor_gt           0.0486
_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^)+(0.0333P)^2^+20.5897P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1026
_refine_ls_wR_factor_ref         0.1185
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13703
_reflns_number_total             18345
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b00856_si_005.cif
_cod_data_source_block           Compound_5
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               4515603
_shelx_shelxl_version_number     2016/6
_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. Restrained distances

 C111-C112

 1.51 with sigma of 0.02

 C104-C105

 1.51 with sigma of 0.02

 C112-C113 \\sim C113-C114 \\sim C114-C115 \\sim C115-C116 \\sim C116-C117

\\sim C117-C112

 with sigma of 0.02

 C112-C116 \\sim C112-C114 \\sim C117-C115 \\sim C113-C117 \\sim C114-C116

\\sim C113-C115

 with sigma of 0.04

 C111-C117 \\sim C111-C113

 with sigma of 0.04

 C105-C106 \\sim C106-C107 \\sim C107-C108 \\sim C108-C109 \\sim C109-C110

\\sim C110-C105

 with sigma of 0.02

 C105-C109 \\sim C105-C107 \\sim C110-C108 \\sim C106-C110 \\sim C107-C109

\\sim C106-C108

 with sigma of 0.04

 C104-C110 \\sim C104-C106

 with sigma of 0.04

3. Restrained planarity

 C111, C112, C113, C114, C115, C116, C117

 with sigma of 0.1

 C104, C105, C106, C107, C108, C109, C110

 with sigma of 0.1

4. Uiso/Uaniso restraints and constraints

C111 \\sim C112 \\sim C113 \\sim C114 \\sim C115 \\sim C116 \\sim C117: within

2A with sigma of 0.04 and sigma for terminal atoms of 0.08

C104 \\sim C105 \\sim C106 \\sim C107 \\sim C108 \\sim C109 \\sim C110: within

2A with sigma of 0.04 and sigma for terminal atoms of 0.08

5. Rigid body (RIGU) restrains

 C111, C112, C113, C114, C115, C116, C117

 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001

 C104, C105, C106, C107, C108, C109, C110

 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001

 C97, C98, C99, C100, C101, C102, C103

 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001

6. Others

 Fixed Sof: C104(0.5) H10A(0.5) H10B(0.5) H10C(0.5) C105(0.5) C106(0.5)

 H106(0.5) C107(0.5) H107(0.5) C108(0.5) H108(0.5) C109(0.5) H109(0.5)

 C110(0.5) H110(0.5) C111(0.5) H11A(0.5) H11B(0.5) H11C(0.5) C112(0.5)

 C113(0.5) H113(0.5) C114(0.5) H114(0.5) C115(0.5) H115(0.5) C116(0.5)

 H116(0.5) C117(0.5) H117(0.5)

7.a Ternary CH refined with riding coordinates:

 C6(H6), C13(H13), C18(H18), C25(H25), C38(H38), C45(H45), C50(H50), C57(H57),

 C70(H70), C77(H77), C82(H82), C89(H89)

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

 C2(H2), C3(H3), C9(H9), C10(H10), C11(H11), C21(H21), C22(H22), C23(H23),

 C28(H28), C30(H30), C31(H31), C32(H32), C34(H34), C35(H35), C41(H41), C42(H42),

  C43(H43), C53(H53), C54(H54), C55(H55), C60(H60), C61(H61), C62(H62),

 C64(H64), C66(H66), C67(H67), C73(H73), C74(H74), C75(H75), C85(H85), C86(H86),

  C87(H87), C92(H92), C93(H93), C94(H94), C96(H96), C99(H99), C100(H100),

 C101(H101), C102(H102), C103(H103), C106(H106), C107(H107), C108(H108),

 C109(H109), C110(H110), C113(H113), C114(H114), C115(H115), C116(H116),

 C117(H117)

7.c Idealised Me refined as rotating group:

 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C),

 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C26(H26A,H26B,H26C), C27(H27A,H27B,

 H27C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C46(H46A,H46B,H46C), C47(H47A,

 H47B,H47C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C58(H58A,H58B,H58C),

 C59(H59A,H59B,H59C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C78(H78A,H78B,

 H78C), C79(H79A,H79B,H79C), C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C90(H90A,

 H90B,H90C), C91(H91A,H91B,H91C), C97(H97A,H97B,H97C), C104(H10A,H10B,H10C),

 C111(H11A,H11B,H11C)

;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a 200 micro/m MITIGEN holder in perfluoroether oil'
_olex2_submission_special_instructions 'No special instructions were received'