Enhanced Electrophilicity of Heterobimetallic Bi-Rh Paddlewheel Carbene Complexes: A Combined Experimental, Spectroscopic, and Computational Study.
Collins, Lee R.; van Gastel, Maurice; Neese, Frank; Fürstner, Alois; Journal of the American Chemical Society 140 (2018) 13042–13055; doi:10.1021/jacs.8b08384

data_4133073
_publ_section_title
;
 Enhanced Electrophilicity of Heterobimetallic Bi-Rh Paddlewheel Carbene
 Complexes: A Combined Experimental, Spectroscopic, and Computational
 Study.
;
_journal_issue                   40
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13042
_journal_page_last               13055
_journal_paper_doi               10.1021/jacs.8b08384
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C32 H41.44 Bi O9 Rh'
_chemical_formula_sum            'C32 H41.44 Bi O9 Rh'
_chemical_formula_weight         881.98
_chemical_name_systematic
;
 bis(mu2-2,2,2',2'-tetramethyl-1,3-benzenedipropanoato-O,O')-aqua-rhodium-
 bismuth
;
_chemical_properties_physical    'air-sensitive, heat-sensitive'
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yc'
_space_group_name_H-M_alt        'P 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_block_code                COM-CA-100-01_10508_RG_100_K
_audit_creation_date             2017-02-16
_audit_creation_method           SHELXL-2018/1
_cell_angle_alpha                90
_cell_angle_beta                 92.199(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.5384(7)
_cell_length_b                   19.201(2)
_cell_length_c                   12.6755(14)
_cell_measurement_reflns_used    9920
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      31.0895
_cell_measurement_theta_min      2.6621
_cell_volume                     1590.2(3)
_computing_cell_refinement       'SAINT software (Bruker AXS, 2004)'
_computing_data_collection       'APEX2 (Bruker AXS, 2005-2013)'
_computing_data_reduction        'SAINT software (Bruker AXS, 2004)'
_computing_molecular_graphics    'DIAMOND (Crystal Impact GbR, 1997-2014)'
_computing_structure_refinement  'SHELXL (G. M. Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (G. M. Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 66.67
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker-AXS Kappa Mach3 APEX-II'
_diffrn_measurement_method       'CCD \f- and \w-scans'
_diffrn_radiation_monochromator  'Incoatec Helios mirrors'
_diffrn_radiation_source         1\mS
_diffrn_radiation_type           Mo-K\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0512
_diffrn_reflns_av_unetI/netI     0.0486
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            44832
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.425
_diffrn_reflns_theta_min         1.060
_exptl_absorpt_coefficient_mu    6.097
_exptl_absorpt_correction_T_max  0.90053
_exptl_absorpt_correction_T_min  0.62391
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   'SADABS (Bruker AXS, 2014/5)'
_exptl_crystal_colour            light-yellow
_exptl_crystal_density_diffrn    1.842
_exptl_crystal_description       prism
_exptl_crystal_F_000             867
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent:  dichloromethane'
_exptl_crystal_size_max          0.103
_exptl_crystal_size_mid          0.062
_exptl_crystal_size_min          0.023
_refine_diff_density_max         1.721
_refine_diff_density_min         -3.904
_refine_diff_density_rms         0.159
_refine_ls_abs_structure_details
;
 Flack x determined using 4265 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.006(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.223
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     469
_refine_ls_number_reflns         10470
_refine_ls_number_restraints     51
_refine_ls_restrained_S_all      1.222
_refine_ls_R_factor_all          0.0476
_refine_ls_R_factor_gt           0.0418
_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^)+7.3772P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0872
_refine_ls_wR_factor_ref         0.0887
_reflns_Friedel_coverage         0.995
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                9690
_reflns_number_total             10470
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b08384_si_002.cif
_cod_data_source_block           BiRhesp2H20
_cod_original_sg_symbol_H-M      'P c'
_cod_database_code               4133073
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_min   0.572
_shelx_estimated_absorpt_t_max   0.872
_shelx_res_checksum              27767
_shelx_hkl_checksum              19241