Mechanistic Investigation of Enantioconvergent Kumada Reactions of Racemic α-Bromoketones Catalyzed by a Nickel/Bis(oxazoline) Complex.
Yin, Haolin; Fu, Gregory C.; Journal of the American Chemical Society 141 (2019) 15433–15440; doi:10.1021/jacs.9b08185

data_4128987
_publ_section_title
;
 Mechanistic Investigation of Enantioconvergent Kumada Reactions of
 Racemic \a-Bromoketones Catalyzed by a Nickel/Bis(oxazoline) Complex.
;
_journal_issue                   38
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              15433
_journal_page_last               15440
_journal_paper_doi               10.1021/jacs.9b08185
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C21 H22 Br2 N2 Ni O2'
_chemical_formula_sum            'C21 H22 Br2 N2 Ni O2'
_chemical_formula_weight         552.94
_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
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-03-05
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   8.9454(9)
_cell_length_b                   11.7746(13)
_cell_length_c                   20.350(3)
_cell_measurement_reflns_used    9730
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      36.36
_cell_measurement_theta_min      2.49
_cell_volume                     2143.4(4)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0384
_diffrn_reflns_av_unetI/netI     0.0227
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            126446
_diffrn_reflns_theta_full        36.36
_diffrn_reflns_theta_max         36.36
_diffrn_reflns_theta_min         2.65
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.652
_exptl_absorpt_correction_T_max  0.7471
_exptl_absorpt_correction_T_min  0.5792
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0940 before and 0.0687 after correction.
The Ratio of minimum to maximum transmission is 0.7753.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.713
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1104
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.390
_refine_diff_density_min         -0.903
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.000(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     256
_refine_ls_number_reflns         10383
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0214
_refine_ls_R_factor_gt           0.0184
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0190P)^2^+0.2220P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0419
_refine_ls_wR_factor_ref         0.0425
_reflns_number_gt                9775
_reflns_number_total             10383
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja9b08185_si_002.cif
_cod_data_source_block           NiBr2
_cod_depositor_comments
;
The following automatic conversions were performed:

data name '_atom_site_symetry_multiplicity' was replaced with
'_atom_site_symmetry_multiplicity' as specified in the replacement
file
'/home/data/users/saulius/crontab/automatic-downloads/current/ACS/lib/lists/replacement-tags.lst'.

Automatic conversion script
Id: cif_correct_tags 6909 2019-04-08 15:41:33Z antanas 
;
_cod_database_code               4128987
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.983(3) 0.017(3)
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
3.a Ternary CH refined with riding coordinates:
 C1(H1), C9(H9)
3.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C8(H8A,H8B)
3.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C17(H17), C18(H18),
 C19(H19), C20(H20), C21(H21)
3.d Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C)
;
_olex2_date_sample_data_collection 2016-08-13
_olex2_date_sample_submission    2016-08-11
_olex2_submission_original_sample_id ((R,R)-Ph-BOX)NiBr2
_olex2_submission_special_instructions 'No special instructions were received'