Molecular hydrogen and water activation by transition metal frustrated Lewis pairs containing ruthenium or osmium components: catalytic hydrogenation assays
Lamata, Pilar; Beard, Sophie; Grasa, Alejandro; Viguri, Fernando; Ricardo, Rodriguez Martinez; López, José A.; Lahoz, Fernando J.; García-Orduña, Pilar; Carmona, Daniel; Dalton Transactions  (2023) –; doi:10.1039/D3DT02339G

data_7713784
_publ_section_title
;
 Molecular hydrogen and water activation by transition metal frustrated
 Lewis pairs containing ruthenium or osmium components: catalytic
 hydrogenation assays
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT02339G
_journal_year                    2023
_chemical_formula_moiety
'C39 H44.93 Cl0.07 N3 P Ru,C39 H44.96 Cl0.04 N3 P Ru,2(F6 Sb)'
_chemical_formula_sum            'C78 H89.89 Cl0.11 F12 N6 P2 Ru2 Sb2'
_chemical_formula_weight         1851.01
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-01-20
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-07-14 deposited with the CCDC.	2023-08-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.768(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.2956(12)
_cell_length_b                   11.7168(5)
_cell_length_c                   24.4621(11)
_cell_measurement_reflns_used    9753
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.28
_cell_measurement_theta_min      2.24
_cell_volume                     7814.3(6)
_computing_cell_refinement       'SAINT V8.40B (Bruker AXS, 2016) in APEX4'
_computing_data_collection       'SAINT V8.40B (Bruker AXS, 2016) in APEX4'
_computing_data_reduction        'SAINT V8.40B (Bruker AXS, 2016) in APEX4'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Photon III'
_diffrn_detector_type            'Bruker Photon III area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'Bruker Photon III , D8 Venture diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0312
_diffrn_reflns_av_unetI/netI     0.0152
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            224868
_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         28.316
_diffrn_reflns_theta_min         1.928
_diffrn_source                   'high brilliance microfocus sealed tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_type              'Diamond  Incoatec Microfocus Source '
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.183
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6912
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS 2016/2: Krause, L., Herbst-Irmer, R., Sheldrick G.M. & Stalke D.,
 J. Appl. Cryst. 48 (2015) 3-10
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.573
_exptl_crystal_description       prism
_exptl_crystal_F_000             3719
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.066
_refine_diff_density_max         1.933
_refine_diff_density_min         -1.241
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.116
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1001
_refine_ls_number_reflns         19415
_refine_ls_number_restraints     200
_refine_ls_restrained_S_all      1.121
_refine_ls_R_factor_all          0.0326
_refine_ls_R_factor_gt           0.0303
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0200P)^2^+13.3834P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0672
_refine_ls_wR_factor_ref         0.0686
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18295
_reflns_number_total             19415
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02339g4.cif
_cod_data_source_block           cmpnd_14
_cod_database_code               7713784
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.926
_shelx_estimated_absorpt_t_min   0.815
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All Ru(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N2-H2 = N3-H3
 0.88 with sigma of 0.02
 N52-H52 = N53-H53
 0.88 with sigma of 0.02
 Sb1A-F1 \\sim Sb1A-F5A \\sim Sb1A-F2A \\sim Sb1A-F6A \\sim Sb1A-F3A \\sim
Sb1A-F4
 with sigma of 0.02
 Sb1B-F2B \\sim Sb1B-F4 \\sim Sb1B-F3B \\sim Sb1B-F6B \\sim Sb1B-F5B \\sim
Sb1B-F1
 with sigma of 0.02
 F2B-F3B \\sim F2B-F6B \\sim F2B-F5B \\sim F4-F1 \\sim F3B-F6B \\sim F3B-F5B
 with sigma of 0.04
 F1-F4 \\sim F5A-F2A \\sim F5A-F3A \\sim F2A-F6A \\sim F2A-F3A \\sim F6A-F3A
 with sigma of 0.04
3. Rigid body (RIGU) restrains
 Sb1A, F5A, F2A, F6A, F3A, F4, F1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F6B, F2B, Sb1B, F5B, F3B, F1, F4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(Cl1B)=1-FVAR(1)
 Sof(H)=FVAR(1)
 Sof(Cl51)=1-FVAR(2)
 Sof(HA)=FVAR(2)
 Sof(F6B)=Sof(F3B)=Sof(Sb1B)=Sof(F2B)=1-FVAR(3)
 Sof(Sb1A)=Sof(F6A)=Sof(F3A)=Sof(F2A)=Sof(F5A)=FVAR(3)
 Fixed Sof: F5B(0.40068)
5.a Riding coordinates:
 Ru1(H), Ru51(HA)
5.b Ternary CH refined with riding coordinates:
 C8(H8), C58(H58)
5.c Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C24(H24A,H24B), C73(H73A,H73B), C74(H74A,H74B)
5.d Aromatic/amide H refined with riding coordinates:
 C2(H2A), C3(H3A), C5(H5), C6(H6), C12(H12), C13(H13), C14(H14), C15(H15),
 C16(H16), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C27(H27), C28(H28),
  C30(H30), C31(H31), C34(H34), C35(H35), C37(H37), C38(H38), C52(H52A),
 C53(H53A), C55(H55), C56(H56), C62(H62), C63(H63), C64(H64), C65(H65),
 C66(H66), C68(H68), C69(H69), C70(H70), C71(H71), C72(H72), C77(H77), C78(H78),
  C80(H80), C81(H81), C84(H84), C85(H85), C87(H87), C88(H88)
5.e Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C32(H32A,H32B,H32C),
 C39(H39A,H39B,H39C), C57(H57A,H57B,H57C), C59(H59A,H59B,H59C), C60(H60A,H60B,
 H60C), C82(H82A,H82B,H82C), C89(H89A,H89B,H89C)
;
_shelx_res_checksum              41615
_olex2_submission_special_instructions 'No special instructions were received'