Cobalt-Catalyzed and Lewis Acid-Assisted Nitrile Hydrogenation to Primary Amines: A Combined Effort
Tokmic, Kenan; Jackson, Bailey J.; Salazar, Andrea; Woods, Toby J.; Fout, Alison R.; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b07368

data_4126410
_publ_contact_author
;
Alison R. Fout 
University of Illinois 
School of Chemical Sciences 
A406 CLSL, Box 54-6 
600 South Mathews Avenue 
Urbana, Illinois  61801 
USA 
;
_publ_section_title
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 Cobalt-Catalyzed and Lewis Acid-Assisted Nitrile Hydrogenation to Primary
 Amines: A Combined Effort
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b07368
_journal_year                    2017
_chemical_formula_moiety         'C63 H53 Co N5 P, C4 H10 O'
_chemical_formula_sum            'C67 H63 Co N5 O P'
_chemical_formula_weight         1044.12
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-02-03
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.322(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.9017(10)
_cell_length_b                   16.1949(10)
_cell_length_c                   18.5938(12)
_cell_measurement_reflns_used    9985
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      25.19
_cell_measurement_theta_min      2.28
_cell_volume                     5381.6(6)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 V2013.10-0 (Bruker, 2013)'
_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      100.0
_diffrn_detector                 'Bruker Photon 100 area detector'
_diffrn_detector_type            'photon counter area detector'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'multilayer mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0983
_diffrn_reflns_av_unetI/netI     0.0490
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            128137
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.438
_diffrn_reflns_theta_max         25.438
_diffrn_reflns_theta_min         1.535
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.398
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8874
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0762 before and 0.0710 after correction.
The Ratio of minimum to maximum transmission is 0.8874.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    1.289
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             2200
_exptl_crystal_id                cm72zsa
_exptl_crystal_size_max          0.416
_exptl_crystal_size_mid          0.064
_exptl_crystal_size_min          0.035
_refine_diff_density_max         0.306
_refine_diff_density_min         -0.412
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     684
_refine_ls_number_reflns         9921
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0648
_refine_ls_R_factor_gt           0.0378
_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^)+(0.0479P)^2^+2.6830P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0890
_refine_ls_wR_factor_ref         0.1073
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7368
_reflns_number_total             9921
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07368_si_002.cif
_cod_data_source_block           cm72zsa
_cod_database_code               4126410
_shelx_estimated_absorpt_t_max   0.986
_shelx_estimated_absorpt_t_min   0.852
_olex2_refinement_description
;
1. 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
2.a Secondary CH2 refined with riding coordinates:
 C65(H65A,H65B), C66(H66A,H66B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C15(H15),
 C16(H16), C17(H17), C18(H18), C23(H23), C25(H25), C32(H32), C34(H34), C40(H40),
  C41(H41), C42(H42), C43(H43), C44(H44), C46(H46), C47(H47), C48(H48),
 C49(H49), C50(H50), C52(H52), C53(H53), C54(H54), C55(H55), C56(H56), C59(H59),
  C60(H60), C61(H61), C62(H62), C63(H63)
2.c Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C36(H36A,H36B,
 H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C64(H64A,H64B,H64C), C67(H67A,
 H67B,H67C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'