Comparison of Reactivity and Enantioselectivity between Chiral Bimetallic Catalysts: Bismuth‒Rhodium- and Dirhodium-Catalyzed Carbene Chemistry
Ren, Zhi; Sunderland, Travis L.; Tortoreto, Cecilia; Yang, Tzuhsiung; Berry, John F.; Musaev, Djamaladdin G.; Davies, Huw M. L.; ACS Catalysis 8 (2018) 10676–; doi:10.1021/acscatal.8b03054

data_4515769
_publ_section_title
;
 Comparison of Reactivity and Enantioselectivity between Chiral Bimetallic
 Catalysts: Bismuth--Rhodium- and Dirhodium-Catalyzed Carbene Chemistry
;
_journal_issue                   11
_journal_name_full               'ACS Catalysis'
_journal_page_first              10676
_journal_paper_doi               10.1021/acscatal.8b03054
_journal_volume                  8
_journal_year                    2018
_chemical_formula_moiety
'C63.36 H86.72 Bi N4 O16.84 Rh S4, 1.12(C4 H8 O)'
_chemical_formula_sum            'C67.84 H95.68 Bi N4 O17.96 Rh S4'
_chemical_formula_weight         1694.73
_space_group_crystal_system      tetragonal
_space_group_IT_number           79
_space_group_name_Hall           'I 4'
_space_group_name_H-M_alt        'I 4'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-07-22
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   22.2169(5)
_cell_length_b                   22.2169(5)
_cell_length_c                   10.9063(3)
_cell_measurement_reflns_used    9912
_cell_measurement_temperature    200(2)
_cell_measurement_theta_max      23.01
_cell_measurement_theta_min      2.59
_cell_volume                     5383.2(2)
_computing_cell_refinement       'SAINT+ Ver. 8.34A (Bruker-AXS, 2014)'
_computing_data_collection       'APEX2 Ver. 2014.11-0 (Bruker-AXS, 2014)'
_computing_data_reduction        'SAINT+ Ver. 8.34A (Bruker-AXS, 2014)'
_computing_molecular_graphics    'OLEX2 (Dolomanov et al., 2009)'
_computing_publication_material  'OLEX2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2015b)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      200.0
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '0.5\% \w and 0.5\% \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_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  0.0346
_diffrn_reflns_av_unetI/netI     0.0314
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            32684
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.284
_diffrn_reflns_theta_min         2.080
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.910
_exptl_absorpt_correction_T_max  0.4803
_exptl_absorpt_correction_T_min  0.4173
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Krause et al., 2015) was used for absorption correction.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.046
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1733
_exptl_crystal_size_max          0.174
_exptl_crystal_size_mid          0.127
_exptl_crystal_size_min          0.107
_refine_diff_density_max         1.473
_refine_diff_density_min         -0.448
_refine_diff_density_rms         0.118
_refine_ls_abs_structure_details
;
 Flack x determined using 2568 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.021(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     275
_refine_ls_number_reflns         6660
_refine_ls_number_restraints     347
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0444
_refine_ls_R_factor_gt           0.0361
_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^)+(0.0647P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0913
_refine_ls_wR_factor_ref         0.0956
_reflns_Friedel_coverage         0.899
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                6051
_reflns_number_total             6660
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b03054_si_002.cif
_cod_data_source_block           berry695
_cod_original_cell_volume        5383.2(3)
_cod_database_code               4515769
_shelx_estimated_absorpt_t_max   0.822
_shelx_estimated_absorpt_t_min   0.732
_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. Restrained distances
 C14A-C12A \\sim C15A-C12A \\sim C14-C12 \\sim C13-C12 \\sim C13A-C12A \\sim
C15-C12
 with sigma of 0.02
 C9-C12A \\sim C9-C12
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C19) = Uanis(C18) = Uanis(C17) = Uanis(C16)
Uanis(C13) = Uanis(C14) = Uanis(C15)
Uanis(C13A) = Uanis(C14A) = Uanis(C15A)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C12A)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14A)=Sof(H14D)=
 Sof(H14E)=Sof(H14F)=Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=1-FVAR(1)
 Sof(C12)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(1)
 Fixed Sof: O5(0.21) C16(0.21) H16A(0.21) H16B(0.21) C17(0.21) H17A(0.21)
 H17B(0.21) C18(0.21) H18A(0.21) H18B(0.21) C19(0.21) H19A(0.21) H19B(0.21)
 O7(0.1) C24(0.1) H24A(0.1) H24B(0.1) C25(0.1) H25A(0.1) H25B(0.1) C26(0.1)
 H26A(0.1) H26B(0.1) C27(0.1) H27A(0.1) H27B(0.1) O6(0.18) C20(0.18) H20A(0.18)
 H20B(0.18) C21(0.18) H21A(0.18) H21B(0.18) C22(0.18) H22A(0.18) H22B(0.18)
 C23(0.18) H23A(0.18) H23B(0.18)
6.a Free rotating group:
 O5(N1,C1,C2,C3,C4,C5,C16,C17,C18,C19), O7(C24,C25,C26,C27), O6(C20,C21,C22,C23)
6.b Ternary CH refined with riding coordinates:
 C2(H2)
6.c Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C16(H16A,H16B), C17(H17A,H17B),
 C18(H18A,H18B), C19(H19A,H19B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B),
  C27(H27A,H27B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B)
6.d Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C10(H10), C11(H11)
6.e Fitted hexagon refined as free rotating group:
 C6(C7,C8,C9,C10,C11)
6.f Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C13A(H13D,H13E,
 H13F), C14A(H14D,H14E,H14F), C15A(H15D,H15E,H15F)
;
_shelx_res_checksum              20138
_shelx_hkl_checksum              2165
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'