Substrate-assisted product release in hydrogenation of LOHCs facilitated by hemilabile pyridine in Ru(ii)–NNC pincer complexes and enhanced activity of proton-responsive protic-NHC ligands
Nath, Shambhu; Singh, Amrendra K.; Catalysis Science & Technology 15 (2025) 2999–3008; doi:10.1039/D5CY00209E

data_1574355
_publ_section_title
;
 Substrate-assisted product release in hydrogenation of LOHCs facilitated
 by hemilabile pyridine in Ru(ii)--NNC pincer complexes and enhanced
 activity of proton-responsive protic-NHC ligands
;
_journal_issue                   10
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              2999
_journal_page_last               3008
_journal_paper_doi               10.1039/D5CY00209E
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety         'C56 H49 N6 P2 Ru, Cl'
_chemical_formula_sum            'C56 H49 Cl N6 P2 Ru'
_chemical_formula_weight         1004.47
_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
_audit_creation_date             2025-02-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2025-02-18 deposited with the CCDC.	2025-04-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.991(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.8637(5)
_cell_length_b                   24.5322(6)
_cell_length_c                   18.1868(5)
_cell_measurement_reflns_used    18872
_cell_measurement_temperature    298.15
_cell_measurement_theta_max      28.4300
_cell_measurement_theta_min      3.3670
_cell_volume                     5393.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_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      298.15
_diffrn_detector_area_resol_mean 16.0309
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.907
_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      8.00  81.00   1.00   26.00    --   18.17-134.00 175.00   73
  2  \w      8.00  82.00   1.00   26.00    --   18.17-135.00  -3.00   74
  3  \w    -82.00 -29.00   1.00   26.00    --  -19.42 134.00-117.00   53
  4  \w    -83.00 -29.00   1.00   26.00    --  -19.42 135.00  62.00   54
  5  \w    -54.00  44.00   1.00   26.00    --   18.17 -37.00 -60.00   98
  6  \w     -3.00  69.00   1.00   26.00    --   18.17  57.00  90.00   72
  7  \w    -43.00  -5.00   1.00   26.00    --   18.17 -77.00  60.00   38
  8  \w     20.00  47.00   1.00   26.00    --   18.17 -77.00  60.00   27
  9  \w    -84.00  11.00   1.00   26.00    --  -19.42 -77.00 150.00   95
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Mo at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0831
_diffrn_reflns_av_unetI/netI     0.0702
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.907
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            61950
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.907
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.235
_diffrn_reflns_theta_min         3.007
_exptl_absorpt_coefficient_mu    0.440
_exptl_absorpt_correction_T_max  0.964
_exptl_absorpt_correction_T_min  0.801
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.237
_exptl_crystal_description       plank
_exptl_crystal_F_000             2072
_exptl_crystal_size_max          0.76
_exptl_crystal_size_mid          0.38
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.875
_refine_diff_density_min         -0.797
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     601
_refine_ls_number_reflns         13286
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0839
_refine_ls_R_factor_gt           0.0564
_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^)+(0.0435P)^2^+4.6391P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1196
_refine_ls_wR_factor_ref         0.1364
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9427
_reflns_number_total             13286
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy00209e2.cif
_cod_data_source_block           aks266b
_cod_depositor_comments
'Adding full bibliography for 1574355--1574356.cif.'
_cod_database_code               1574355
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.949
_shelx_estimated_absorpt_t_min   0.731
_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 Aromatic/amide H refined with riding coordinates:
 C44(H44), C56(H56), C52(H52), C20(H20), C17(H17), C54(H54), C5(H5), C50(H50),
 C10(H10), C26(H26), C40(H40), C55(H55), C15(H15), C22(H22), C7(H7), C46(H46),
 C18(H18), C6(H6), C3(H3), C53(H53), C19(H19), C28(H28), C38(H38), C43(H43),
 C49(H49), C32(H32), C48(H48), C47(H47), C11(H11), C41(H41), C14(H14), C42(H42),
  C36(H36), C37(H37), C23(H23), C29(H29), C31(H31), C25(H25), C30(H30),
 C34(H34), C24(H24), C35(H35)
2.b Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C13(H13A,H13B,H13C)
;
_shelx_res_checksum              66493
_shelx_fab_checksum              72103
_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
;