Rapid and selective formic acid dehydrogenation catalysis by molecular ruthenium hydrides supported by rigid PCcarbeneP pincer ligands
Donnelly, Laurie J.; Gelfand, Benjamin S.; Piers, Warren E.; Catalysis Science & Technology 15 (2025) 100–106; doi:10.1039/D4CY01346H

data_1573308
_publ_section_title
;
 Rapid and selective formic acid dehydrogenation catalysis by molecular
 ruthenium hydrides supported by rigid PCcarbeneP pincer ligands
;
_journal_issue                   1
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              100
_journal_page_last               106
_journal_paper_doi               10.1039/D4CY01346H
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety         'C39 H55 Cl N2 O2 P2 Ru'
_chemical_formula_sum            'C39 H55 Cl N2 O2 P2 Ru'
_chemical_formula_weight         782.31
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-11-24
_audit_creation_method
;
Olex2 1.5
(compiled 2021.11.18 svn.ra9532c28 for OlexSys, GUI svn.r6429)
;
_audit_update_record
;
2024-11-05 deposited with the CCDC.	2024-11-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.8540(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.6687(7)
_cell_length_b                   15.5241(10)
_cell_length_c                   22.9366(15)
_cell_measurement_reflns_used    9128
_cell_measurement_temperature    173.0
_cell_measurement_theta_max      27.881
_cell_measurement_theta_min      2.318
_cell_volume                     3794.1(4)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_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    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      173.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f 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  0.0388
_diffrn_reflns_av_unetI/netI     0.0249
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            56196
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.479
_diffrn_reflns_theta_min         1.585
_diffrn_source                   'fine focus X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_type              Siemens
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.604
_exptl_absorpt_correction_T_max  0.0955
_exptl_absorpt_correction_T_min  0.0660
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0489 before and 0.0426 after correction.
The Ratio of minimum to maximum transmission is 0.6911.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.370
_exptl_crystal_description       block
_exptl_crystal_F_000             1640
_exptl_crystal_size_max          0.263
_exptl_crystal_size_mid          0.116
_exptl_crystal_size_min          0.071
_refine_diff_density_max         1.771
_refine_diff_density_min         -0.861
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     438
_refine_ls_number_reflns         8690
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0542
_refine_ls_R_factor_gt           0.0444
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0555P)^2^+8.5535P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1195
_refine_ls_wR_factor_ref         0.1257
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7234
_reflns_number_total             8690
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cy01346h3.cif
_cod_data_source_block           ld290
_cod_depositor_comments          'Adding full bibliography for 1573308.cif.'
_cod_database_code               1573308
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.958
_shelx_estimated_absorpt_t_min   0.857
_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:
 C16(H16), C19(H19), C28(H28), C31(H31)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C10(H10), C12(H12), C35(H35), C36(H36), C37(H37), C38(H38),
 C39(H39)
2.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C20(H20A,H20B,
 H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,
 H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C),
 C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              29754
_shelx_hkl_checksum              54743
_olex2_submission_special_instructions 'No special instructions were received'