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_1552033
_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
'C37 H37 Cl2 P Rh2 Si2, 1.5(C H2 Cl2), C0.5 Cl, C0.55 H0.72 Cl1'
_chemical_formula_sum            'C39.55 H40.72 Cl7 P Rh2 Si2'
_chemical_formula_weight         1057.19
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 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
_cell_angle_beta                 99.837(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.3566(4)
_cell_length_b                   13.3287(3)
_cell_length_c                   23.2251(7)
_cell_measurement_reflns_used    40301
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.7600
_cell_measurement_theta_min      3.0980
_cell_volume                     4378.9(2)
_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
_diffrn_detector                 'Oxford Diffraction Sapphire 3'
_diffrn_detector_area_resol_mean 8.26
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.990
_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    -39.00  48.00   1.00   26.24    --  -20.71  57.00   0.00   87
  2  \w    -25.00  20.00   1.00   26.24    --  -20.71 -99.00 150.00   45
  3  \w     -7.00  90.00   1.00   26.24    --   21.18  77.00  90.00   97
  4  \w    -49.00  43.00   1.00   26.24    --   21.18 -38.00-180.00   92
  5  \w    -48.00  50.00   1.00   26.24    --   21.18 -77.00-120.00   98
  6  \w     -1.00  92.00   1.00   26.24    --   21.18  38.00-180.00   93
  7  \w    -25.00  62.00   1.00   26.24    --   21.18 -99.00 -30.00   87
  8  \w    -71.00   9.00   1.00   26.24    --  -20.71 118.00  27.00   80
  9  \w    -25.00  20.00   1.00   26.24    --  -20.71 -99.00 -30.00   45
 10  \w      3.00  90.00   1.00   26.24    --   21.18  57.00-120.00   87
 11  \w    -47.00  40.00   1.00   26.24    --   21.18 -57.00 150.00   87
 12  \w     34.00  95.00   1.00   26.24    --   21.18 179.00-180.00   61
 13  \w     -1.00  92.00   1.00   26.24    --   21.18  38.00 -30.00   93
 14  \w      3.00  52.00   1.00   26.24    --   21.18  57.00  30.00   49
;
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Oxford Diffraction Xcalibur S'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0006147000
_diffrn_orient_matrix_UB_12      0.0124400000
_diffrn_orient_matrix_UB_13      0.0296242000
_diffrn_orient_matrix_UB_21      -0.0092928000
_diffrn_orient_matrix_UB_22      0.0508020000
_diffrn_orient_matrix_UB_23      -0.0080759000
_diffrn_orient_matrix_UB_31      -0.0492762000
_diffrn_orient_matrix_UB_32      -0.0097869000
_diffrn_orient_matrix_UB_33      -0.0042495000
_diffrn_radiation_collimation    0.3
_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  0.0508
_diffrn_reflns_av_unetI/netI     0.0312
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            113012
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.033
_diffrn_reflns_theta_min         2.880
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.300
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.68234
_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    1.604
_exptl_crystal_description       block
_exptl_crystal_F_000             2120
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.005
_refine_diff_density_min         -0.726
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.235
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     516
_refine_ls_number_reflns         12695
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.235
_refine_ls_R_factor_all          0.0511
_refine_ls_R_factor_gt           0.0429
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0165P)^2^+6.4992P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0725
_refine_ls_wR_factor_ref         0.0746
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11579
_reflns_number_total             12695
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc02683e2.cif
_cod_data_source_block           exp_4891
_cod_database_code               1552033
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C60H60Rh4P2Si2Cl4
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_olex2_refinement_description
;
1. Others
 Fixed Sof: C9(0.5)
 Fixed Uiso: H00M(0.031) H00O(0.023) H00R(0.024) H00T(0.027) H00U(0.033)
 H00V(0.028) H00W(0.029) H00X(0.022) H00Y(0.032) H00Z(0.03) H010(0.032)
 H011(0.038) H012(0.037) H01A(0.054) H01B(0.054) H01C(0.054) H014(0.038)
 H01D(0.059) H01E(0.059) H01F(0.059) H01G(0.059) H01H(0.059) H01I(0.059)
 H017(0.042) H018(0.051) H01J(0.076) H01K(0.076) H01L(0.076) H01M(0.048)
 H01N(0.073) H01O(0.073) H01P(0.073) H01Q(0.076) H01R(0.076) H01S(0.076)
 H01V(0.073) H01W(0.073) H01T(0.055) H01U(0.065) H01X(0.066) H01Y(0.066)
 H01Z(0.106) H(0.106)
 Fixed X: H00M(0.728119) H00O(0.904739) H00R(0.755543) H00T(0.867894)
 H00U(0.509362) H00V(0.959845) H00W(0.825793) H00X(0.819546) H00Y(1.064445)
 H00Z(1.035179) H010(0.885544) H011(0.682924) H012(0.69949) H01A(0.532644)
 H01B(0.597669) H01C(0.623284) H014(0.408199) H01D(0.911837) H01E(0.935705)
 H01F(0.948839) H01G(0.647567) H01H(0.73279) H01I(0.71847) H017(0.441701)
 H018(0.770902) H01J(0.818608) H01K(0.787275) H01L(0.825849) H01M(0.578254)
 H01N(0.822292) H01O(0.80359) H01P(0.718404) H01Q(0.647144) H01R(0.606124)
 H01S(0.547858) H01V(0.35179) H01W(0.34498) H01T(0.738064) H01U(0.773122)
 H01X(0.523336) H01Y(0.620728) H01Z(0.63555) H(0.524882)
 Fixed Y: H00M(0.271625) H00O(0.414259) H00R(0.777573) H00T(0.573477)
 H00U(0.317158) H00V(0.353104) H00W(0.847821) H00X(0.428605) H00Y(0.294087)
 H00Z(0.321859) H010(0.745144) H011(0.51317) H012(0.238247) H01A(0.837988)
 H01B(0.923951) H01C(0.811515) H014(0.323675) H01D(0.39635) H01E(0.465767)
 H01F(0.505707) H01G(0.452529) H01H(0.440159) H01I(0.363135) H017(0.428141)
 H018(0.10486) H01J(0.856611) H01K(0.966294) H01L(0.895324) H01M(0.522895)
 H01N(0.684569) H01O(0.651191) H01P(0.669243) H01Q(0.923509) H01R(0.996868)
 H01S(0.902468) H01V(0.755033) H01W(0.693219) H01T(0.070216) H01U(0.003824)
 H01X(0.772089) H01Y(0.72929) H01Z(0.712482) H(0.721908)
 Fixed Z: H00M(0.477005) H00O(0.568822) H00R(0.432557) H00T(0.298655)
 H00U(0.328757) H00V(0.381532) H00W(0.359111) H00X(0.338723) H00Y(0.460548)
 H00Z(0.554551) H010(0.293871) H011(0.269532) H012(0.303133) H01A(0.608465)
 H01B(0.638865) H01C(0.653782) H014(0.24003) H01D(0.685642) H01E(0.740677)
 H01F(0.679082) H01G(0.716518) H01H(0.76808) H01I(0.716308) H017(0.166955)
 H018(0.489369) H01J(0.622281) H01K(0.603816) H01L(0.559461) H01M(0.181143)
 H01N(0.688521) H01O(0.75026) H01P(0.699348) H01Q(0.468927) H01R(0.511066)
 H01S(0.485892) H01V(0.446523) H01W(0.388605) H01T(0.316137) H01U(0.408498)
 H01X(0.326042) H01Y(0.315546) H01Z(0.311772) H(0.296336)
;
_shelx_res_checksum              56551
_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 1.568
_oxdiff_exptl_absorpt_empirical_full_min 0.657