Cyclometalated Iridium-PhanePhos Complexes Are Active Catalysts in Enantioselective Allene-Fluoral Reductive Coupling and Related Alcohol-Mediated Carbonyl Additions That Form Acyclic Quaternary Carbon Stereocenters.
Schwartz, Leyah A.; Holmes, Michael; Brito, Gilmar A.; Gonçalves, Théo P; Richardson, Jeffery; Ruble, J. Craig; Huang, Kuo-Wei; Krische, Michael J.; Journal of the American Chemical Society 141 (2019) 2087–2096; doi:10.1021/jacs.8b11868

data_4127920
_publ_section_title
;
 Cyclometalated Iridium-PhanePhos Complexes Are Active Catalysts in
 Enantioselective Allene-Fluoral Reductive Coupling and Related
 Alcohol-Mediated Carbonyl Additions That Form Acyclic Quaternary Carbon
 Stereocenters.
;
_journal_issue                   5
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              2087
_journal_page_last               2096
_journal_paper_doi               10.1021/jacs.8b11868
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H14 Br F3 N2 O6'
_chemical_formula_sum            'C19 H14 Br F3 N2 O6'
_chemical_formula_weight         503.23
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2016/6
_cell_angle_alpha                90
_cell_angle_beta                 94.863(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.4648(11)
_cell_length_b                   7.4731(7)
_cell_length_c                   11.5835(11)
_cell_measurement_reflns_used    9853
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.3
_cell_measurement_theta_min      2.61
_cell_volume                     988.87(16)
_computing_cell_refinement       'Apex II release 2010, Bruker AXS, Inc.'
_computing_data_collection       'Apex II release 2010, Bruker AXS, Inc.'
_computing_data_reduction        'Apex II release 2010, Bruker AXS, Inc.'
_computing_molecular_graphics    'XP SHELXTL/PC, Siemens Analytical'
_computing_publication_material  'SHELXL-2016/6, Sheldrick, G. M.'
_computing_structure_refinement  'Shelxl-2016/6, Sheldrick, G. M.'
_computing_structure_solution
;

Sheldrick, G. M. (2015).  SHELXT.  Acta Cryst. A71, 3-8.

;
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Nonius Kappa CCD with Bruker Apex II detector'
_diffrn_measurement_method       \w-scans
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0407
_diffrn_reflns_av_unetI/netI     0.0471
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            30981
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.525
_diffrn_reflns_theta_min         2.400
_diffrn_source                   'sealed fine focus tube'
_exptl_absorpt_coefficient_mu    2.147
_exptl_absorpt_correction_T_max  0.7386
_exptl_absorpt_correction_T_min  0.6021
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   'SADABS 2014/5'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.690
_exptl_crystal_description       prisms
_exptl_crystal_F_000             504
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.340
_refine_diff_density_min         -0.382
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 2185 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.034(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.998
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     281
_refine_ls_number_reflns         5960
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.998
_refine_ls_R_factor_all          0.0324
_refine_ls_R_factor_gt           0.0261
_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^)+(0.0210P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0524
_refine_ls_wR_factor_ref         0.0537
_reflns_Friedel_coverage         0.846
_reflns_Friedel_fraction_full    0.982
_reflns_Friedel_fraction_max     0.969
_reflns_number_gt                5336
_reflns_number_total             5960
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b11868_si_003.cif
_cod_data_source_block           shelx
_cod_database_code               4127920
_shelx_shelxl_version_number     2016/6
_shelx_res_checksum              36629
_shelx_hkl_checksum              73834