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_7713788
_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 H44.85 Cl0.15 N3 Os P,C39 H44.70 Cl0.30 N3 Os P,2(F6 Sb)'
_chemical_formula_sum            'C78 H89.55 Cl0.45 F12 N6 Os2 P2 Sb2'
_chemical_formula_weight         2040.98
_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             2023-01-23
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-06 deposited with the CCDC.	2023-08-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.223(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.612(4)
_cell_length_b                   11.6966(18)
_cell_length_c                   24.349(4)
_cell_measurement_reflns_used    9844
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.413
_cell_measurement_theta_min      2.471
_cell_volume                     7843(2)
_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_area_resol_mean 7.9
_diffrn_detector_type            'Bruker Photon III area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.978
_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_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0396
_diffrn_reflns_av_unetI/netI     0.0154
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -37
_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            324467
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.689
_diffrn_reflns_theta_min         2.047
_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
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.042
_exptl_absorpt_correction_T_max  0.6655
_exptl_absorpt_correction_T_min  0.5153
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1056 before and 0.0565 after correction.
The Ratio of minimum to maximum transmission is 0.7743.
The \l/2 correction factor is Not present.

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    1.729
_exptl_crystal_description       prism
_exptl_crystal_F_000             3997
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: THF'
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.083
_refine_diff_density_max         2.072
_refine_diff_density_min         -1.563
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.154
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1079
_refine_ls_number_reflns         19814
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.154
_refine_ls_R_factor_all          0.0344
_refine_ls_R_factor_gt           0.0322
_refine_ls_shift/su_max          0.006
_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^+26.6685P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0732
_refine_ls_wR_factor_ref         0.0744
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18902
_reflns_number_total             19814
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02339g4.cif
_cod_data_source_block           cmpnd_15
_cod_database_code               7713788
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.730
_shelx_estimated_absorpt_t_min   0.530
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All Os(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C60B) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C60A) \\sim Ueq, Uanis(C60B) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
3. Rigid body (RIGU) restrains
 C53A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C60B, C58B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C60A, C58A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C60B)=Sof(H60A)=Sof(H60B)=Sof(H60C)=Sof(C51B)=Sof(C52B)=Sof(H52B)=
 Sof(C53B)=Sof(H53B)=Sof(C54B)=Sof(C55B)=Sof(H55B)=Sof(C56B)=Sof(H56B)=
 Sof(C57B)=Sof(H57D)=Sof(H57E)=Sof(H57F)=Sof(C58B)=Sof(H58B)=Sof(C59B)=
 Sof(H59D)=Sof(H59E)=Sof(H59F)=1-FVAR(1)
 Sof(C51A)=Sof(C52A)=Sof(H52A)=Sof(C53A)=Sof(H53A)=Sof(C54A)=Sof(C55A)=
 Sof(H55A)=Sof(C56A)=Sof(H56A)=Sof(C57A)=Sof(H57A)=Sof(H57B)=Sof(H57C)=
 Sof(C58A)=Sof(H58A)=Sof(C59A)=Sof(H59A)=Sof(H59B)=Sof(H59C)=Sof(C60A)=
 Sof(H60D)=Sof(H60E)=Sof(H60F)=FVAR(1)
 Sof(Cl1B)=Sof(F8B)=Sof(F10B)=Sof(F11B)=Sof(F12B)=1-FVAR(2)
 Sof(H)=Sof(F8A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=FVAR(2)
 Sof(Cl51)=1-FVAR(3)
 Sof(HA)=FVAR(3)
5.a Riding coordinates:
 Os1(H), Os51(HA)
5.b Ternary CH refined with riding coordinates:
 C8(H8), C58A(H58A), C58B(H58B)
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:
 N2(H2), N3(H3), 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), N52(H52), N53(H53), 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), C52A(H52A),
 C53A(H53A), C55A(H55A), C56A(H56A), C52B(H52B), C53B(H53B), C55B(H55B),
 C56B(H56B)
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), C82(H82A,H82B,H82C), C89(H89A,H89B,H89C), C57A(H57A,H57B,
 H57C), C59A(H59A,H59B,H59C), C60B(H60A,H60B,H60C), C57B(H57D,H57E,H57F),
 C59B(H59D,H59E,H59F), C60A(H60D,H60E,H60F)
;
_shelx_res_checksum              353
_olex2_submission_special_instructions 'No special instructions were received'