Low-valent Homobimetallic Rh Complexes: Influence of Ligands on the Structure and the Intramolecular Reactivity of Rh‒H Intermediates
Jurt, Pascal; Salnikov, Oleg; Gianetti, Thomas L.; Chukanov, Nikita; Baker, Matthew G.; Le Corre, Grégoire; Borger, Jaap E.; Verel, René; Gauthier, Sébastien; Fuhr, Olaf; Kovtunov, Kirill V.; Fedorov, Alexey; Fenske, Dieter; Koptyug, Igor V.; Grützmacher, Hansjörg; Chemical Science  (2019) –; doi:10.1039/C9SC02683E

data_1552034
_publ_section_title
;
 Low-valent Homobimetallic Rh Complexes: Influence of Ligands on the
 Structure and the Intramolecular Reactivity of Rh--H Intermediates
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC02683E
_journal_year                    2019
_chemical_formula_moiety
'C63 H59 F3 O3 P3 Rh2 S Si2, C F3 O3 S, 3(C H2 Cl2)'
_chemical_formula_sum            'C67 H65 Cl6 F6 O6 P3 Rh2 S2 Si2'
_chemical_formula_weight         1711.92
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-06-08
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2019-05-29 deposited with the CCDC.    2019-07-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 115.129(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.6773(5)
_cell_length_b                   20.3524(4)
_cell_length_c                   21.3813(5)
_cell_measurement_reflns_used    21744
_cell_measurement_temperature    153.15
_cell_measurement_theta_max      63.15
_cell_measurement_theta_min      2.61
_cell_volume                     7358.4(3)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      153.15
_diffrn_detector                 Pilatus300K
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            DECTRIS
_diffrn_measured_fraction_theta_full 0.833
_diffrn_measured_fraction_theta_max 0.946
_diffrn_measurement_device       '4-circle goniometer'
_diffrn_measurement_device_type  'Stoe StadiVari'
_diffrn_measurement_method       'rotation method'
_diffrn_radiation_collimation    '2.5 mm diameter, monocapillary'
_diffrn_radiation_monochromator  'multilayer optics'
_diffrn_radiation_polarisn_norm  0
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54186
_diffrn_reflns_av_R_equivalents  0.0518
_diffrn_reflns_av_unetI/netI     0.0514
_diffrn_reflns_Laue_measured_fraction_full 0.833
_diffrn_reflns_Laue_measured_fraction_max 0.946
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            26080
_diffrn_reflns_point_group_measured_fraction_full 0.833
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        67.686
_diffrn_reflns_theta_max         62.491
_diffrn_reflns_theta_min         2.613
_diffrn_source                   'Cu Genix 3D'
_diffrn_source_current           1.000
_diffrn_source_power             0.050
_diffrn_source_target            Cu
_diffrn_source_type              'microfocus sealed X-ray tube'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    7.634
_exptl_absorpt_correction_T_max  0.7018
_exptl_absorpt_correction_T_min  0.4114
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details   'Stoe Xred and LANA'
_exptl_crystal_colour            'orangish red'
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.545
_exptl_crystal_description       plank
_exptl_crystal_F_000             3464
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.696
_refine_diff_density_min         -0.827
_refine_diff_density_rms         0.126
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     846
_refine_ls_number_reflns         11101
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0899
_refine_ls_R_factor_gt           0.0652
_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^)+(0.1192P)^2^+9.7647P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1713
_refine_ls_wR_factor_ref         0.1845
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8355
_reflns_number_total             11101
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc02683e2.cif
_cod_data_source_block           pj3-51
_cod_database_code               1552034
_shelxl_version_number           2014-3
_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
 Cl5A-C68A = Cl6A-C68A
 1.76 with sigma of 0.02
 Cl5B-Cl6B
 2.9 with sigma of 0.02
 Cl5B-C68B = Cl6B-C68B
 1.76 with sigma of 0.02
 Cl5A-Cl6A
 2.9 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl3 \\sim Cl4 \\sim C67: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
Uiso(C68B) = Uiso(Cl5B) = Uiso(Cl6B)
Uiso(C68A) = Uiso(Cl5A) = Uiso(Cl6A)
4. Others
 Fixed Sof: Cl5A(0.6) Cl6A(0.6) C68A(0.6) H68A(0.6) H68B(0.6) Cl5B(0.4)
 Cl6B(0.4) C68B(0.4) H68C(0.4) H68D(0.4)
5.a Ternary CH refined with riding coordinates:
 C13(H13)
5.b Secondary CH2 refined with riding coordinates:
 C50(H50A,H50B), C66(H66A,H66B), C67(H67A,H67B), C68A(H68A,H68B), C68B(H68C,
 H68D)
5.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C15(H15), C16(H16), C17(H17), C18(H18),
 C27(H27), C28(H28), C29(H29), C30(H30), C31(H31), C33(H33), C34(H34), C35(H35),
  C36(H36), C37(H37), C39(H39), C40(H40), C41(H41), C42(H42), C43(H43),
 C45(H45), C46(H46), C47(H47), C48(H48), C49(H49), C52(H52), C53(H53), C54(H54),
  C55(H55), C56(H56), C59(H59), C60(H60), C61(H61), C62(H62), C63(H63)
5.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C23(H23A,H23B,H23C),
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              39375
_olex2_submission_special_instructions 'No special instructions were received'