Elucidation of a Redox-Mediated Reaction Cycle for Nickel-Catalyzed Cross Coupling.
Sun, Rui; Qin, Yangzhong; Ruccolo, Serge; Schnedermann, Christoph; Costentin, Cyrille; Daniel G Nocera, ?; Journal of the American Chemical Society 141 (2019) 89–93; doi:10.1021/jacs.8b11262

data_4133573
_publ_section_title
;
 Elucidation of a Redox-Mediated Reaction Cycle for Nickel-Catalyzed Cross
 Coupling.
;
_journal_issue                   1
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              89
_journal_page_last               93
_journal_paper_doi               10.1021/jacs.8b11262
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         '2(C50 H74 Cl2 N6 Ni2), 2(Cl), 7(C2 H3 N)'
_chemical_formula_sum            'C114 H169 Cl6 N19 Ni4'
_chemical_formula_weight         2253.21
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-08-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   28.293(3)
_cell_length_b                   12.7260(16)
_cell_length_c                   33.847(4)
_cell_measurement_reflns_used    3922
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.02
_cell_measurement_theta_min      2.31
_cell_volume                     12187(2)
_computing_cell_refinement       'SAINT V8.35A (?, 2016)'
_computing_data_collection       'APEX3 v2016 1.0 (Bruker-AXS,2016)'
_computing_data_reduction        'SAINT V8.35A (Bruker-AXS, 2016)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.01
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'omega and phi scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0702
_diffrn_reflns_av_unetI/netI     0.0598
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            95575
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.052
_diffrn_reflns_theta_max         25.052
_diffrn_reflns_theta_min         1.439
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.792
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6708
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    1.228
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             4800
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.182
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.519
_refine_diff_density_min         -0.531
_refine_diff_density_rms         0.072
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.60(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1743
_refine_ls_number_reflns         21501
_refine_ls_number_restraints     1851
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0832
_refine_ls_R_factor_gt           0.0600
_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^)+(0.0488P)^2^+23.9874P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1334
_refine_ls_wR_factor_ref         0.1421
_reflns_Friedel_coverage         0.963
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                16797
_reflns_number_total             21501
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b11262_si_002.cif
_cod_data_source_block           Complex1_corrected
_cod_database_code               4133573
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.897
_shelx_estimated_absorpt_t_min   0.693
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.40(2)
 0.60(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
3. Restrained distances
 C1YB-C2YB \\sim C1YA-C2YA
 with sigma of 0.02
 N18B-C2YB \\sim N18A-C2YA
 with sigma of 0.02
 C81A-C79A \\sim C81B-C79B \\sim C82A-C79A \\sim C82B-C79B \\sim C80A-C79A
\\sim C80B-C79B
 with sigma of 0.02
 C33-C34A \\sim C33-C34B \\sim C33-C35A \\sim C33-C35B \\sim C33-C36A \\sim
C33-C36B
 with sigma of 0.02
 C5XB-C6XB \\sim C5XA-C6XA
 with sigma of 0.02
 N15A-C6XA \\sim N15B-C6XB
 with sigma of 0.02
 C83-C85A \\sim C83-C85B \\sim C83-C84B \\sim C83-C84A \\sim C83-C86B \\sim
C83-C86A
 with sigma of 0.02
 C15B-C8 \\sim C15A-C8
 with sigma of 0.02
4. Rigid bond restraints
 N18A, C1YA, C2YA, N18B, C1YB, C2YB
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
N18A \\sim C1YA \\sim C2YA \\sim N18B \\sim C1YB \\sim C2YB: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04
C79A \\sim C79B \\sim C80A \\sim C80B \\sim C81A \\sim C81B \\sim C82A \\sim
C82B: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
N13 \\sim C1X \\sim C2X \\sim N14 \\sim C3X \\sim C4X \\sim N16 \\sim C7X \\sim
C8X \\sim N17 \\sim C9X \\sim C10X \\sim N18A \\sim C1YA \\sim C2YA \\sim N19
\\sim C3Y \\sim C4Y: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08
C44A \\sim C44B \\sim C45A \\sim C45B \\sim C46A \\sim C46B \\sim C47A \\sim
C47B \\sim C48A \\sim C48B \\sim C49A \\sim C49B \\sim C50: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C33 \\sim C34A \\sim C34B \\sim C35A \\sim C35B \\sim C36A \\sim C36B: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02
N15A \\sim C5XA \\sim C6XA \\sim N15B \\sim C5XB \\sim C6XB: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04
C11A \\sim C11B \\sim C12A \\sim C12B \\sim C13 \\sim C14A \\sim C14B: within
2A with sigma of 0.02 and sigma for terminal atoms of 0.04
C83 \\sim C84A \\sim C84B \\sim C85A \\sim C85B \\sim C86A \\sim C86B: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C0AA \\sim C15A \\sim C15B \\sim C16 \\sim C17A \\sim C17B \\sim C18B: within
2A with sigma of 0.02 and sigma for terminal atoms of 0.04
C61A \\sim C61B \\sim C62A \\sim C62B \\sim C63A \\sim C63B \\sim C64A \\sim
C64B: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
N11 \\sim C87A \\sim C87B \\sim C88A \\sim C88B \\sim C89A \\sim C89B \\sim
C90A \\sim C90B \\sim C91A \\sim C91B \\sim C92A \\sim C92B \\sim C93A \\sim
C93B: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
6. Rigid body (RIGU) restrains
 N6, C44A, C44B, C45A, C45B, C46A, C46B, C47A, C47B, C48A, C48B, C49A, C49B, C50
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C79A, C79B, C80A, C80B, C81A, C81B, C82A, C82B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C29, C30, C31, C32
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C33, C34A, C34B, C35A, C35B, C36A, C36B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N15A, C5XA, C6XA, N15B, C5XB, C6XB
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C11A, C11B, C12A, C12B, C13, C14A, C14B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C83, C84A, C84B, C85A, C85B, C86A, C86B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C0AA, C15A, C15B, C16, C17A, C17B, C18B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C61A, C61B, C62A, C62B, C63A, C63B, C64A, C64B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N5, C37A, C37B, C38A, C38B, C39A, C39B, C40A, C40B, C41A, C41B, C42A, C42B, C43
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N11, C87A, C87B, C88A, C88B, C89A, C89B, C90A, C90B, C91A, C91B, C92A, C92B,
 C93A, C93B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Same fragment restrains
{N5, C37A, C38A, C39A, C40A, C41A, C42A, C43} sigma for 1-2: 0.02, 1-3: 0.04
as
{N5, C37B, C38B, C39B, C40B, C41B, C42B, C43}
{N6, C44A, C45A, C46A, C47A, C48A, C49A, C50} sigma for 1-2: 0.02, 1-3: 0.04
as
{N6, C44B, C45B, C46B, C47B, C48B, C49B, C50}
{C11A, C12A, C13, C14A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C11B, C12B, C13, C14B}
{C15A, C17A, C0AA} sigma for 1-2: 0.02, 1-3: 0.04
as
{C15B, C17B, C18B}
{N11, C87A, C88A, C89A, C90A, C91A, C92A, C93A} sigma for 1-2: 0.02, 1-3: 0.04
as
{N11, C87B, C88B, C89B, C90B, C91B, C92B, C93B}
{C61A, C62A, C63A, C64A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C61B, C62B, C63B, C64B}
8. Others
 Sof(C37B)=Sof(H37A)=Sof(H37B)=Sof(C38B)=Sof(H38A)=Sof(H38B)=Sof(C39B)=
 Sof(H39A)=Sof(H39B)=Sof(C40B)=Sof(H40A)=Sof(H40B)=Sof(C41B)=Sof(H41A)=
 Sof(H41B)=Sof(C42B)=Sof(H42A)=Sof(H42B)=Sof(H43A)=1-FVAR(1)
 Sof(H43)=Sof(C37A)=Sof(H37C)=Sof(H37D)=Sof(C38A)=Sof(H38C)=Sof(H38D)=
 Sof(C39A)=Sof(H39C)=Sof(H39D)=Sof(C40A)=Sof(H40C)=Sof(H40D)=Sof(C41A)=
 Sof(H41C)=Sof(H41D)=Sof(C42A)=Sof(H42C)=Sof(H42D)=FVAR(1)
 Sof(C44B)=Sof(H44A)=Sof(H44B)=Sof(C45B)=Sof(H45A)=Sof(H45B)=Sof(C46B)=
 Sof(H46A)=Sof(H46B)=Sof(C47B)=Sof(H47A)=Sof(H47B)=Sof(C48B)=Sof(H48A)=
 Sof(H48B)=Sof(C49B)=Sof(H49A)=Sof(H49B)=Sof(H50A)=1-FVAR(2)
 Sof(H50)=Sof(C44A)=Sof(H44C)=Sof(H44D)=Sof(C45A)=Sof(H45C)=Sof(H45D)=
 Sof(C46A)=Sof(H46C)=Sof(H46D)=Sof(C47A)=Sof(H47C)=Sof(H47D)=Sof(C48A)=
 Sof(H48C)=Sof(H48D)=Sof(C49A)=Sof(H49C)=Sof(H49D)=FVAR(2)
 Sof(C87B)=Sof(H87A)=Sof(H87B)=Sof(C88B)=Sof(H88A)=Sof(H88B)=Sof(C89B)=
 Sof(H89A)=Sof(H89B)=Sof(C90B)=Sof(H90A)=Sof(H90B)=Sof(C91B)=Sof(H91A)=
 Sof(H91B)=Sof(C92B)=Sof(H92A)=Sof(H92B)=Sof(C93B)=Sof(H93B)=1-FVAR(3)
 Sof(C87A)=Sof(H87C)=Sof(H87D)=Sof(C88A)=Sof(H88C)=Sof(H88D)=Sof(C89A)=
 Sof(H89C)=Sof(H89D)=Sof(C90A)=Sof(H90C)=Sof(H90D)=Sof(C91A)=Sof(H91C)=
 Sof(H91D)=Sof(C92A)=Sof(H92C)=Sof(H92D)=Sof(C93A)=Sof(H93A)=FVAR(3)
 Sof(C79B)=Sof(C80B)=Sof(H80D)=Sof(H80E)=Sof(H80F)=Sof(C81B)=Sof(H81D)=
 Sof(H81E)=Sof(H81F)=Sof(C82B)=Sof(H82D)=Sof(H82E)=Sof(H82F)=1-FVAR(4)
 Sof(C79A)=Sof(C80A)=Sof(H80A)=Sof(H80B)=Sof(H80C)=Sof(C81A)=Sof(H81A)=
 Sof(H81B)=Sof(H81C)=Sof(C82A)=Sof(H82A)=Sof(H82B)=Sof(H82C)=FVAR(4)
 Sof(N18B)=Sof(C1YB)=Sof(H1YD)=Sof(H1YE)=Sof(H1YF)=Sof(C2YB)=1-FVAR(5)
 Sof(N18A)=Sof(C1YA)=Sof(H1YA)=Sof(H1YB)=Sof(H1YC)=Sof(C2YA)=FVAR(5)
 Sof(C15B)=Sof(C17B)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18B)=Sof(H18A)=
 Sof(H18B)=Sof(H18C)=Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(6)
 Sof(C0AA)=Sof(H0AA)=Sof(H0AB)=Sof(H0AC)=Sof(C15A)=Sof(H16A)=Sof(H16B)=
 Sof(H16C)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=FVAR(6)
 Sof(C11B)=Sof(C12B)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(H13D)=Sof(H13E)=
 Sof(H13F)=Sof(C14B)=Sof(H14A)=Sof(H14B)=Sof(H14C)=1-FVAR(7)
 Sof(C11A)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C12A)=Sof(H12D)=Sof(H12E)=
 Sof(H12F)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=FVAR(7)
 Sof(N15B)=Sof(C5XB)=Sof(H5XD)=Sof(H5XE)=Sof(H5XF)=Sof(C6XB)=1-FVAR(8)
 Sof(N15A)=Sof(C5XA)=Sof(H5XA)=Sof(H5XB)=Sof(H5XC)=Sof(C6XA)=FVAR(8)
 Sof(C34B)=Sof(H34D)=Sof(H34E)=Sof(H34F)=Sof(C35B)=Sof(H35D)=Sof(H35E)=
 Sof(H35F)=Sof(C36B)=Sof(H36D)=Sof(H36E)=Sof(H36F)=1-FVAR(9)
 Sof(C34A)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C35A)=Sof(H35A)=Sof(H35B)=
 Sof(H35C)=Sof(C36A)=Sof(H36A)=Sof(H36B)=Sof(H36C)=FVAR(9)
 Sof(C84B)=Sof(H84D)=Sof(H84E)=Sof(H84F)=Sof(C85B)=Sof(H85D)=Sof(H85E)=
 Sof(H85F)=Sof(C86B)=Sof(H86D)=Sof(H86E)=Sof(H86F)=1-FVAR(10)
 Sof(C84A)=Sof(H84A)=Sof(H84B)=Sof(H84C)=Sof(C85A)=Sof(H85A)=Sof(H85B)=
 Sof(H85C)=Sof(C86A)=Sof(H86A)=Sof(H86B)=Sof(H86C)=FVAR(10)
 Sof(C61B)=Sof(C62B)=Sof(H62A)=Sof(H62B)=Sof(H62C)=Sof(C63B)=Sof(H63A)=
 Sof(H63B)=Sof(H63C)=Sof(C64B)=Sof(H64A)=Sof(H64B)=Sof(H64C)=1-FVAR(11)
 Sof(C61A)=Sof(C62A)=Sof(H62D)=Sof(H62E)=Sof(H62F)=Sof(C63A)=Sof(H63D)=
 Sof(H63E)=Sof(H63F)=Sof(C64A)=Sof(H64D)=Sof(H64E)=Sof(H64F)=FVAR(11)
9.a Ternary CH refined with riding coordinates:
 C43(H43), C43(H43A), C50(H50), C50(H50A), C93B(H93B), C93A(H93A), C100(H100)
9.b Secondary CH2 refined with riding coordinates:
 C37B(H37A,H37B), C38B(H38A,H38B), C39B(H39A,H39B), C40B(H40A,H40B), C41B(H41A,
 H41B), C42B(H42A,H42B), C44B(H44A,H44B), C45B(H45A,H45B), C46B(H46A,H46B),
 C47B(H47A,H47B), C48B(H48A,H48B), C49B(H49A,H49B), C37A(H37C,H37D), C38A(H38C,
 H38D), C39A(H39C,H39D), C40A(H40C,H40D), C41A(H41C,H41D), C42A(H42C,H42D),
 C44A(H44C,H44D), C45A(H45C,H45D), C46A(H46C,H46D), C47A(H47C,H47D), C48A(H48C,
 H48D), C49A(H49C,H49D), C87B(H87A,H87B), C88B(H88A,H88B), C89B(H89A,H89B),
 C90B(H90A,H90B), C91B(H91A,H91B), C92B(H92A,H92B), C87A(H87C,H87D), C88A(H88C,
 H88D), C89A(H89C,H89D), C90A(H90C,H90D), C91A(H91C,H91D), C92A(H92C,H92D),
 C94(H94A,H94B), C95(H95A,H95B), C96(H96A,H96B), C97(H97A,H97B), C98(H98A,H98B),
  C99(H99A,H99B)
9.c Me refined with riding coordinates:
 C0AA(H0AA,H0AB,H0AC), C17B(H17A,H17B,H17C), C18B(H18A,H18B,H18C), C16(H16A,
 H16B,H16C), C16(H16D,H16E,H16F), C17A(H17D,H17E,H17F), C62B(H62A,H62B,H62C),
 C63B(H63A,H63B,H63C), C64B(H64A,H64B,H64C), C62A(H62D,H62E,H62F), C63A(H63D,
 H63E,H63F), C64A(H64D,H64E,H64F)
9.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C7(H7), C9(H9), C10(H10), C19(H19), C20(H20),
 C22(H22), C25(H25), C27(H27), C28(H28), C51(H51), C52(H52), C54(H54), C57(H57),
  C59(H59), C60(H60), C69(H69), C70(H70), C72(H72), C75(H75), C77(H77), C78(H78)
9.e Idealised Me refined as rotating group:
 C12B(H12A,H12B,H12C), C13(H13A,H13B,H13C), C13(H13D,H13E,H13F), C14B(H14A,
 H14B,H14C), C12A(H12D,H12E,H12F), C14A(H14D,H14E,H14F), C30(H30A,H30B,H30C),
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C34A(H34A,H34B,H34C), C34B(H34D,H34E,
 H34F), C35A(H35A,H35B,H35C), C35B(H35D,H35E,H35F), C36A(H36A,H36B,H36C),
 C36B(H36D,H36E,H36F), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C68(H68A,H68B,
 H68C), C80A(H80A,H80B,H80C), C80B(H80D,H80E,H80F), C81A(H81A,H81B,H81C),
 C81B(H81D,H81E,H81F), C82A(H82A,H82B,H82C), C82B(H82D,H82E,H82F), C84A(H84A,
 H84B,H84C), C84B(H84D,H84E,H84F), C85A(H85A,H85B,H85C), C85B(H85D,H85E,H85F),
 C86A(H86A,H86B,H86C), C86B(H86D,H86E,H86F), C1X(H1XA,H1XB,H1XC), C3X(H3XA,H3XB,
 H3XC), C5XA(H5XA,H5XB,H5XC), C5XB(H5XD,H5XE,H5XF), C7X(H7XA,H7XB,H7XC),
 C9X(H9XA,H9XB,H9XC), C1YA(H1YA,H1YB,H1YC), C1YB(H1YD,H1YE,H1YF), C3Y(H3YA,H3YB,
 H3YC)
;
_shelx_res_checksum              62466
_shelx_hkl_checksum              79111
_olex2_submission_special_instructions 'No special instructions were received'