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_1574356
_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         'C55 H46 N6 P2 Ru, C H4 O'
_chemical_formula_sum            'C56 H50 N6 O P2 Ru'
_chemical_formula_weight         986.03
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -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                102.178(2)
_cell_angle_beta                 107.581(2)
_cell_angle_gamma                95.342(2)
_cell_formula_units_Z            2
_cell_length_a                   13.4509(3)
_cell_length_b                   14.0264(3)
_cell_length_c                   14.3050(2)
_cell_measurement_reflns_used    29915
_cell_measurement_temperature    298.15
_cell_measurement_theta_max      29.0070
_cell_measurement_theta_min      3.4220
_cell_volume                     2479.06(9)
_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 0.920
_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    -20.00  60.00   1.00   15.00    --   18.17 -99.00 -76.00   80
  2  \w    -61.00  -1.00   1.00   15.00    --  -19.42  99.00  30.00   60
  3  \w     -8.00  91.00   1.00   15.00    --   18.17  37.00  60.00   99
  4  \w    -12.00  88.00   1.00   15.00    --   18.17  77.00  60.00  100
  5  \w    -12.00  88.00   1.00   15.00    --   18.17  77.00 150.00  100
  6  \w    -54.00  44.00   1.00   15.00    --   18.17 -37.00-120.00   98
  7  \w     34.00  95.00   1.00   15.00    --   18.17-178.00 -90.00   61
  8  \w    -52.00  48.00   1.00   15.00    --   18.17 -77.00 -30.00  100
  9  \w    -20.00  60.00   1.00   15.00    --   18.17 -99.00 120.00   80
 10  \w    -88.00   2.00   1.00   15.00    --  -19.42 -57.00  60.00   90
 11  \w    -49.00  51.00   1.00   15.00    --  -19.42  77.00   0.00  100
 12  \w     -3.00  49.00   1.00   15.00    --   18.17  57.00 -90.00   52
 13  \w     -3.00  87.00   1.00   15.00    --   18.17  57.00 -60.00   90
;
_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  0.0517
_diffrn_reflns_av_unetI/netI     0.0394
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.920
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            55217
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.920
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.197
_diffrn_reflns_theta_min         3.014
_exptl_absorpt_coefficient_mu    0.426
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85089
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.321
_exptl_crystal_description       rhombohedral
_exptl_crystal_F_000             1020
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.445
_refine_diff_density_min         -0.604
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     602
_refine_ls_number_reflns         12367
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0431
_refine_ls_R_factor_gt           0.0345
_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^)+(0.0385P)^2^+0.4698P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0856
_refine_ls_wR_factor_ref         0.0916
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10590
_reflns_number_total             12367
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy00209e2.cif
_cod_data_source_block           red1
_cod_depositor_comments
'Adding full bibliography for 1574355--1574356.cif.'
_cod_database_code               1574356
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.923
_shelx_estimated_absorpt_t_min   0.841
_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, All O(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C25(H25), C14(H14), C2(H2), C21(H21), C19(H19), C45(H45), C4(H4), C24(H24),
 C31(H31), C16(H16), C18(H18), C51(H51), C39(H39), C13(H13), C17(H17), C5(H5),
 C27(H27), C37(H37), C23(H23), C33(H33), C55(H55), C9(H9), C43(H43), C6(H6),
 C49(H49), C22(H22), C52(H52), C30(H30), C28(H28), C47(H47), C29(H29), C10(H10),
  C48(H48), C53(H53), C46(H46), C36(H36), C34(H34), C54(H54), C42(H42),
 C40(H40), C41(H41), C35(H35)
2.b Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C56(H56A,H56B,H56C)
2.c Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              57609
_shelx_fab_checksum              15616
_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
;