Photoredox-Assisted Reductive Cross-Coupling: Mechanistic Insight into Catalytic Aryl-Alkyl Cross-Couplings.
Paul, Avishek; Smith, Mark D.; Vannucci, Aaron K.; The Journal of organic chemistry 82 (2017) 1996–2003; doi:10.1021/acs.joc.6b02830

data_4032272
_publ_section_title
;
 Photoredox-Assisted Reductive Cross-Coupling: Mechanistic Insight into
 Catalytic Aryl-Alkyl Cross-Couplings.
;
_journal_issue                   4
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              1996
_journal_page_last               2003
_journal_paper_doi               10.1021/acs.joc.6b02830
_journal_volume                  82
_journal_year                    2017
_chemical_formula_moiety         'C24 H22 N6 Ni, 2(F6 P)'
_chemical_formula_sum            'C24 H22 F12 N6 Ni P2'
_chemical_formula_weight         743.12
_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             2015-07-16
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                65.204(2)
_cell_angle_beta                 69.405(2)
_cell_angle_gamma                66.420(2)
_cell_formula_units_Z            2
_cell_length_a                   11.0651(7)
_cell_length_b                   11.7597(7)
_cell_length_c                   13.8038(8)
_cell_measurement_reflns_used    9523
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.52
_cell_measurement_theta_min      2.21
_cell_volume                     1457.44(16)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'Bruker APEXII v2014.9-0 (Bruker, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker PHOTON-100 area detector'
_diffrn_detector_area_resol_mean 10.4
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Quest'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0330
_diffrn_reflns_av_unetI/netI     0.0168
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            56094
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        27.560
_diffrn_reflns_theta_max         27.559
_diffrn_reflns_theta_min         2.210
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.880
_exptl_absorpt_correction_T_max  0.5630
_exptl_absorpt_correction_T_min  0.5051
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.1265 before and 0.0482 after correction.
The Ratio of minimum to maximum transmission is 0.8972.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'light purple'
_exptl_crystal_density_diffrn    1.693
_exptl_crystal_description       plate
_exptl_crystal_F_000             748
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.163
_refine_diff_density_min         -0.565
_refine_diff_density_rms         0.086
_refine_ls_extinction_coef       0.0038(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     457
_refine_ls_number_reflns         6723
_refine_ls_number_restraints     253
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0499
_refine_ls_R_factor_gt           0.0441
_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^)+(0.0562P)^2^+2.8606P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1131
_refine_ls_wR_factor_ref         0.1175
_reflns_number_gt                6022
_reflns_number_total             6723
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b02830_si_001.cif
_cod_data_source_block           avi_2b_0m
_cod_database_code               4032272
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.966
_shelx_estimated_absorpt_t_min   0.803
_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. Uiso/Uaniso restraints and constraints
Uanis(P3A) = Uanis(P3B) = Uanis(P3C)
Uanis(F33A) = Uanis(F33B) = Uanis(F33C)
Uanis(F31A) = Uanis(F31B) = Uanis(F31C)
Uanis(F36A) = Uanis(F36B) = Uanis(F36C)
Uanis(F32A) = Uanis(F32B) = Uanis(F32C)
Uanis(F34A) = Uanis(F34B) = Uanis(F34C)
Uanis(F35A) = Uanis(F35B) = Uanis(F35C)
3. Rigid body (RIGU) restrains
 P3A, F31A, F32A, F33A, F34A, F35A, F36A, P3B, F31B, F32B, F33B, F34B, F35B,
 F36B, P3C, F31C, F32C, F33C, F34C, F35C, F36C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Same fragment restrains
{P3A, F31A, F32A, F33A, F34A, F35A, F36A} sigma for 1-2: 0.02, 1-3: 0.04
as
{P3B, F31B, F32B, F33B, F34B, F35B, F36B}
{P3A, F31A, F32A, F33A, F34A, F35A, F36A} sigma for 1-2: 0.02, 1-3: 0.04
as
{P3C, F31C, F32C, F33C, F34C, F35C, F36C}
5. Others
 1*[Sof(P3A)+Sof(F31A)+Sof(F32A)+Sof(F33A)+Sof(F34A)+Sof(F35A)+Sof(F36A)]+1*
 [Sof(P3B)+Sof(F31B)+Sof(F32B)+Sof(F33B)+Sof(F34B)+Sof(F35B)+Sof(F36B)]+1*
 [Sof(P3C)+Sof(F31C)+Sof(F32C)+Sof(F33C)+Sof(F34C)+Sof(F35C)+Sof(F36C)]=1 with
 esd of 0.0001
 Sof(P3A)=Sof(F31A)=Sof(F32A)=Sof(F33A)=Sof(F34A)=Sof(F35A)=Sof(F36A)=FVAR(1)
 Sof(P3B)=Sof(F31B)=Sof(F32B)=Sof(F33B)=Sof(F34B)=Sof(F35B)=Sof(F36B)=FVAR(2)
 Sof(P3C)=Sof(F31C)=Sof(F32C)=Sof(F33C)=Sof(F34C)=Sof(F35C)=Sof(F36C)=FVAR(3)
6.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C12(H12), C13(H13),
 C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C20(H20)
6.b Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              32546
_shelx_hkl_checksum              12077
_olex2_submission_special_instructions 'No special instructions were received'