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_1552037
_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         'C39 H37 F6 O6 P Rh2 S2 Si2'
_chemical_formula_sum            'C39 H37 F6 O6 P Rh2 S2 Si2'
_chemical_formula_weight         1072.78
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-05-29 deposited with the CCDC.    2019-07-08 downloaded from the CCDC.
;
_cell_angle_alpha                90.049(2)
_cell_angle_beta                 96.419(2)
_cell_angle_gamma                91.948(2)
_cell_formula_units_Z            2
_cell_length_a                   10.5393(3)
_cell_length_b                   13.5890(4)
_cell_length_c                   15.1402(4)
_cell_measurement_reflns_used    15752
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      32.3570
_cell_measurement_theta_min      3.0590
_cell_volume                     2153.49(11)
_computing_cell_refinement       'CrysAlis RED, Oxford Diffraction Ltd.'
_computing_data_collection       'CrysAlis CCD, Oxford Diffraction Ltd.'
_computing_data_reduction        'CrysAlis RED, Oxford Diffraction Ltd.'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Oxford Diffraction Sapphire 3'
_diffrn_detector_area_resol_mean 8.26
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -63.00  47.00   1.00    2.42    --  -25.15  19.00 150.00  110
  2  \w    -54.00  44.00   1.00    2.42    --  -25.15  77.00 -30.00   98
  3  \w   -100.00 -32.00   1.00    2.42    --  -25.15 179.00-180.00   68
  4  \w    -94.00  -7.00   1.00    2.42    --  -25.15 -57.00 -30.00   87
  5  \w    -94.00   3.00   1.00    2.42    --  -25.15 -77.00-150.00   97
  6  \w      0.00  83.00   1.00    2.42    --   25.62-129.00 179.00   83
  7  \w    -25.00  66.00   1.00    2.42    --   25.62 -99.00  30.00   91
  8  \w    -94.00   3.00   1.00    2.42    --  -25.15 -77.00  30.00   97
  9  \w    -94.00  -7.00   1.00    2.42    --  -25.15 -57.00 120.00   87
 10  \w    -94.00  -7.00   1.00    2.42    --  -25.15 -57.00 -90.00   87
 11  \w    -94.00  -7.00   1.00    2.42    --  -25.15 -57.00  60.00   87
 12  \w    -44.00  54.00   1.00    2.42    --   25.62 -77.00-120.00   98
 13  \w     34.00 100.00   1.00    2.42    --   25.62 179.00 -60.00   66
 14  \w      3.00  49.00   1.00    2.42    --   25.62  38.00-180.00   46
;
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Oxford Diffraction Xcalibur S'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0152109000
_diffrn_orient_matrix_UB_12      -0.0300316000
_diffrn_orient_matrix_UB_13      0.0377406000
_diffrn_orient_matrix_UB_21      -0.0022800000
_diffrn_orient_matrix_UB_22      0.0414956000
_diffrn_orient_matrix_UB_23      0.0281594000
_diffrn_orient_matrix_UB_31      -0.0659960000
_diffrn_orient_matrix_UB_32      -0.0101946000
_diffrn_orient_matrix_UB_33      0.0023094000
_diffrn_radiation_monochromator  'focusing graphite'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0560
_diffrn_reflns_av_unetI/netI     0.0490
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            67993
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.506
_diffrn_reflns_theta_min         2.871
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.026
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68585
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.23a (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.654
_exptl_crystal_description       plate
_exptl_crystal_F_000             1076
_exptl_crystal_recrystallization_method 'DCM layer hexane'
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.757
_refine_diff_density_min         -0.577
_refine_diff_density_rms         0.108
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     529
_refine_ls_number_reflns         14224
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0503
_refine_ls_R_factor_gt           0.0334
_refine_ls_shift/su_max          0.238
_refine_ls_shift/su_mean         0.009
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0250P)^2^+0.8500P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0660
_refine_ls_wR_factor_ref         0.0735
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11441
_reflns_number_total             14224
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc02683e2.cif
_cod_data_source_block           pjxr08_2
_cod_depositor_comments
;

2025-06-17
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum
'C8.67 H8.22 F1.33 O1.33 P0.22 Rh0.44 S0.44 Si0.44'
_cod_original_formula_weight         238.39
_cod_original_formula_moiety         '0.22(C39 H37 F6 O6 P Rh2 S2 Si2)'
_cod_original_formula_units_Z            9
_cod_database_code               1552037
_shelx_shelxl_version_number     2017/1
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C010(H010)
2.b Aromatic/amide H refined with riding coordinates:
 C00S(H00S), C00W(H00W), C00X(H00X), C011(H011), C012(H012), C013(H013),
 C014(H014), C016(H016), C017(H017), C019(H019), C01B(H01G), C01C(H01H),
 C01F(H01O), C01H(H01S), C01J(H01W), C01K(H01X), C01L(H01Y), C01M(H01Z)
2.c Idealised Me refined as rotating group:
 C018(H01A,H01B,H01C), C01A(H01D,H01E,H01F), C01D(H01I,H01J,H01K), C01E(H01L,
 H01M,H01N), C01G(H01P,H01Q,H01R), C01I(H01T,H01U,H01V)
;
_shelx_res_checksum              11714
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.415
_oxdiff_exptl_absorpt_empirical_full_min 0.676