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_1552035
_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
'0.5(C55 H53 P2 Rh Si2), 0.5(C F3 O3 S), 0.5(C4 H7.03 O), 0.74(C4 H8 O)'
_chemical_formula_sum            'C32.95 H34.41 F1.5 O2.74 P Rh0.5 S0.5 Si'
_chemical_formula_weight         629.29
_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             2019-02-13
_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                82.096(2)
_cell_angle_beta                 83.193(2)
_cell_angle_gamma                72.058(2)
_cell_formula_units_Z            4
_cell_length_a                   13.5229(13)
_cell_length_b                   14.4511(13)
_cell_length_c                   16.9413(16)
_cell_measurement_reflns_used    9328
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.23
_cell_measurement_theta_min      2.35
_cell_volume                     3109.6(5)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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_temperature      100.01
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0468
_diffrn_reflns_av_unetI/netI     0.0353
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            76568
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.102
_diffrn_reflns_theta_min         1.490
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.456
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.344
_exptl_crystal_description       block
_exptl_crystal_F_000             1308
_exptl_crystal_recrystallization_method 'Cryst THF layer hexane'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.955
_refine_diff_density_min         -1.171
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     765
_refine_ls_number_reflns         13682
_refine_ls_number_restraints     68
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0682
_refine_ls_R_factor_gt           0.0459
_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^)+(0.0618P)^2^+4.9822P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1120
_refine_ls_wR_factor_ref         0.1303
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10722
_reflns_number_total             13682
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc02683e2.cif
_cod_data_source_block           pjmonorh_1_0m
_cod_original_formula_sum        'C32.95 H34.41 F1.50 O2.74 P Rh0.50 S0.50 Si'
_cod_database_code               1552035
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.956
_shelx_estimated_absorpt_t_min   0.914
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H5AA,HE,HF} of C01Z, All C(H,H) groups, All C(H,H,H,H)
  groups
 At 1.5 times of:
  {H01A,H01B,H01C} of C017, {H2AA,H,HA} of C01V, {H01J,H01K,H01L} of C01H,
  {H3AA,HB,HC} of C01W, {H01V,H01W,H01X} of C01P, {H01M,H01N,H01O} of C01I
2. Restrained distances
 O01Y-C022
 1.42 with sigma of 0.001
 O01Y-C026
 1.42 with sigma of 0.001
 C1_1-C2_1 \\sim C2_1-C3_1 \\sim C3_1-C4_1
 with sigma of 0.02
 O1_1-C1_1 \\sim O1_1-C4_1
 with sigma of 0.02
 O1_1-C2_1 \\sim O1_1-C3_1
 with sigma of 0.04
 C2_1-C4_1 \\sim C1_1-C3_1
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O1_1 \\sim C1_1 \\sim C2_1 \\sim C3_1 \\sim C4_1: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 O1_1, C1_1, C2_1, C3_1, C4_1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(HF)=Sof(H02C)=Sof(H02D)=Sof(C029)=Sof(H029)=1-FVAR(1)
 Sof(H5AA)=Sof(HE)=Sof(H02A)=Sof(H02B)=Sof(C028)=Sof(H02E)=Sof(H02F)=FVAR(1)
 Sof(O1)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(H3A)=
 Sof(H3B)=Sof(C4)=Sof(H4A)=Sof(H4B)=0.5*FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C00S(H00S)
6.b Secondary CH2 refined with riding coordinates:
 C01X(H4AA,HD), C01Z(H5AA,HE), C021(H02A,H02B), C021(H02C,H02D), C022(H02G,
 H02H), C023(H02I,H02J), C024(H02K,H02L), C026(H02M,H02N), C028(H02E,H02F),
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B)
6.c Aromatic/amide H refined with riding coordinates:
 C00L(H00L), C00N(H00N), C00P(H00P), C00R(H00R), C00T(H00T), C00W(H00W),
 C00X(H00X), C00Y(H00Y), C00Z(H00Z), C011(H011), C012(H012), C013(H013),
 C014(H014), C015(H015), C016(H016), C018(H018), C019(H019), C01A(H01D),
 C01C(H01E), C01D(H01F), C01E(H01G), C01F(H01H), C01G(H01I), C01J(H01P),
 C01K(H01Q), C01L(H01R), C01M(H01S), C01N(H01T), C01O(H01U), C01Q(H01Y),
 C01R(H01Z), C01S(H01), C01T(H0AA), C01U(H1AA), C01Z(HF), C029(H029)
6.d Idealised Me refined as rotating group:
 C017(H01A,H01B,H01C), C01H(H01J,H01K,H01L), C01I(H01M,H01N,H01O), C01P(H01V,
 H01W,H01X), C01V(H2AA,H,HA), C01W(H3AA,HB,HC)
;
_shelx_res_checksum              89882
_olex2_submission_special_instructions 'No special instructions were received'