Ligand flexibility as a concept to unlock catalytic activity: acyclic carbenes for base-free transfer ruthenium hydrogenation catalysis.
Righetti, Gianluca; Koidan, Georgyi; Filimonchuk, Sergiy L.; Shishkina, Svitlana; Kostyuk, Aleksandr; Albrecht, Martin; Chemical science 17 (2026) 4325–4331; doi:10.1039/d5sc08206d

data_1576684
_publ_section_title
;
 Ligand flexibility as a concept to unlock catalytic activity: acyclic
 carbenes for base-free transfer ruthenium hydrogenation catalysis.
;
_journal_issue                   8
_journal_name_full               'Chemical science'
_journal_page_first              4325
_journal_page_last               4331
_journal_paper_doi               10.1039/d5sc08206d
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C12 H17 Cl2 N Ru'
_chemical_formula_sum            'C12 H17 Cl2 N Ru'
_chemical_formula_weight         347.23
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-01-13T14:26:26-00:00
_audit_update_record
;
2025-09-11 deposited with the CCDC.	2025-12-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.3053(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.55034(8)
_cell_length_b                   11.01135(5)
_cell_length_c                   12.79041(5)
_cell_measurement_reflns_used    48461
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      80.339
_cell_measurement_theta_min      3.534
_cell_volume                     2717.23(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.95a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.136a 64-bit (release 23-08-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.95a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1
_diffrn_measured_fraction_theta_max 1
_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    -68.00  22.00   0.50    0.50    --  -49.99  74.00 126.00  180
  2  \w   -121.00 -32.00   0.50    0.50    --  -49.99 -74.00  -1.00  178
  3  \w    -21.00  68.00   0.50    0.50    --   49.99 -74.00  -1.00  178
  4  \w    -96.00 -18.00   0.50    0.80    --  -90.00  74.00 126.00  156
  5  \w   -161.00 -72.00   0.50    0.80    --  -90.00 -74.00  -1.00  178
  6  \w     93.00 177.00   0.50    0.80    --  111.50  74.00 126.00  168
  7  \w     41.00  96.00   0.50    0.80    --  111.50 -74.00  -1.00  110
  8  \w     93.00 177.00   0.50    0.80    --  111.50  74.00 126.00  168
  9  \w   -119.00 -73.00   0.50    0.50    --  -49.99-125.00 120.00   92
 10  \w   -119.00 -73.00   0.50    0.50    --  -49.99-125.00  60.00   92
 11  \w    -98.00 -43.00   0.50    0.50    --  -49.99   0.00   0.00  110
 12  \w    -22.00  26.00   0.50    0.50    --   49.99 -19.00   0.00   96
 13  \w    -21.00  43.00   0.50    0.50    --   49.99 -38.00 120.00  128
 14  \w     32.00 122.00   0.50    0.50    --   49.99  74.00 126.00  180
 15  \w   -161.00 -86.00   0.50    0.80    --  -90.00 -15.00-150.00  150
 16  \w    -51.00 -18.00   0.50    0.80    --  -90.00  45.00  60.00   66
 17  \w   -160.00 -82.00   0.50    0.80    --  -90.00 -45.00 -60.00  156
 18  \w    -71.00 -18.00   0.50    0.80    --  -90.00  61.00-120.00  106
 19  \w   -138.00 -83.00   0.50    0.80    --  -90.00   0.00-150.00  110
 20  \w    108.00 177.00   0.50    0.80    --  111.50  30.00 -90.00  138
 21  \w     92.00 162.00   0.50    0.80    --  111.50  77.00-180.00  140
 22  \w     99.00 173.00   0.50    0.80    --  111.50  61.00-150.00  148
 23  \w     45.00  70.00   0.50    0.80    --  111.50 -61.00-120.00   50
 24  \w     50.00 101.00   0.50    0.80    --  111.50-125.00 150.00  102
 25  \w     43.00  68.00   0.50    0.80    --  111.50 -61.00 -60.00   50
 26  \w     41.00  67.00   0.50    0.80    --  111.50 -61.00-180.00   52
 27  \w    104.00 141.00   0.50    0.80    --  111.50  45.00  60.00   74
 28  \w     43.00  89.00   0.50    0.80    --  111.50-125.00  30.00   92
 29  \w     47.00 107.00   0.50    0.80    --  111.50-125.00 120.00  120
 30  \w     50.00 104.00   0.50    0.80    --  111.50 -77.00 -60.00  108
 31  \w     46.00  74.00   0.50    0.80    --  111.50-125.00-150.00   56
 32  \w     44.00  76.00   0.50    0.80    --  111.50-125.00  90.00   64
 33  \w     79.00 108.00   0.50    0.80    --  111.50-125.00  90.00   58
 34  \w     43.00  81.00   0.50    0.80    --  111.50-125.00   0.00   76
 35  \w    106.00 132.00   0.50    0.80    --  111.50  77.00-120.00   52
 36  \w    132.00 176.00   0.50    0.80    --  111.50  45.00-180.00   88
 37  \w     98.00 131.00   0.50    0.80    --  111.50  61.00  30.00   66
 38  \w    137.00 176.00   0.50    0.80    --  111.50  61.00  30.00   78
 39  \w     62.00 104.00   0.50    0.80    --  111.50 -77.00-120.00   84
 40  \w    106.00 159.00   0.50    0.80    --  111.50  45.00-120.00  106
 41  \w    138.00 163.00   0.50    0.80    --  111.50  77.00 150.00   50
 42  \w    111.00 176.00   0.50    0.80    --  111.50  45.00 120.00  130
 43  \w     93.00 136.00   0.50    0.80    --  111.50  77.00 150.00   86
 44  \w     41.00  70.00   0.50    0.80    --  111.50 -61.00 -90.00   58
 45  \w     45.00  96.00   0.50    0.80    --  111.50 -77.00-150.00  102
 46  \w     70.00  96.00   0.50    0.80    --  111.50 -77.00  60.00   52
 47  \w     44.00  70.00   0.50    0.80    --  111.50 -61.00  30.00   52
 48  \w    142.00 176.00   0.50    0.80    --  111.50  77.00-120.00   68
 49  \w    111.00 136.00   0.50    0.80    --  111.50  45.00 -60.00   50
 50  \w    139.00 176.00   0.50    0.80    --  111.50  45.00 -60.00   74
 51  \w     42.00  68.00   0.50    0.80    --  111.50 -61.00   0.00   52
 52  \w     98.00 161.00   0.50    0.80    --  111.50  61.00  60.00  126
 53  \w     49.00 106.00   0.50    0.80    --  111.50 -94.00   0.00  114
 54  \w     44.00  70.00   0.50    0.80    --  111.50 -61.00 150.00   52
 55  \w    109.00 147.00   0.50    0.80    --  111.50  30.00 120.00   76
 56  \w    100.00 127.00   0.50    0.80    --  111.50  61.00-120.00   54
 57  \w    132.00 163.00   0.50    0.80    --  111.50  61.00-120.00   62
 58  \w     41.00  67.00   0.50    0.80    --  111.50 -61.00  60.00   52
 59  \w     41.00  67.00   0.50    0.80    --  111.50 -77.00 120.00   52
 60  \w     42.00  68.00   0.50    0.80    --  111.50 -94.00  60.00   52
 61  \w    126.00 154.00   0.50    0.80    --  111.50 125.00-180.00   56
 62  \w     98.00 151.00   0.50    0.80    --  111.50  77.00  60.00  106
 63  \w     65.00 100.00   0.50    0.80    --  111.50   0.00 120.00   70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0605674
_diffrn_orient_matrix_UB_12      -0.0532079
_diffrn_orient_matrix_UB_13      -0.0787524
_diffrn_orient_matrix_UB_21      -0.0085961
_diffrn_orient_matrix_UB_22      -0.1018902
_diffrn_orient_matrix_UB_23      0.0793967
_diffrn_orient_matrix_UB_31      -0.0513516
_diffrn_orient_matrix_UB_32      0.0797714
_diffrn_orient_matrix_UB_33      0.0488264
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0267
_diffrn_reflns_av_unetI/netI     0.0211
_diffrn_reflns_Laue_measured_fraction_full 1
_diffrn_reflns_Laue_measured_fraction_max 1
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            56430
_diffrn_reflns_point_group_measured_fraction_full 1
_diffrn_reflns_point_group_measured_fraction_max 1
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.487
_diffrn_reflns_theta_min         2.29
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.731
_exptl_absorpt_correction_T_max  0.683
_exptl_absorpt_correction_T_min  0.113
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.43.95a (Rigaku Oxford Diffraction, 2023)
        Numerical absorption correction based on gaussian integration over
        a multifaceted crystal model
        Empirical absorption correction using spherical harmonics,
        implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.698
_exptl_crystal_description       block
_exptl_crystal_F_000             1392
_exptl_crystal_size_max          0.249
_exptl_crystal_size_mid          0.164
_exptl_crystal_size_min          0.064
_refine_diff_density_max         0.782
_refine_diff_density_min         -0.414
_refine_diff_density_rms         0.069
_refine_ls_extinction_coef       0.000426(19)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.186
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     298
_refine_ls_number_reflns         5543
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.186
_refine_ls_R_factor_all          0.0209
_refine_ls_R_factor_gt           0.0208
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0252P)^2^+2.1381P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0565
_refine_ls_wR_factor_ref         0.0566
_reflns_Friedel_coverage         0
_reflns_number_gt                5512
_reflns_number_total             5543
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08206d2.cif
_cod_data_source_block           Ru-1
_cod_depositor_comments
'Adding full bibliography for 1576683--1576688.cif.'
_cod_database_code               1576684
_shelx_estimated_absorpt_t_min   0.143
_shelx_estimated_absorpt_t_max   0.515
_oxdiff_exptl_absorpt_empirical_details
;
        Empirical correction (ABSPACK) includes:
        - Absorption correction using spherical harmonics
        - Frame scaling
        - Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.405
_oxdiff_exptl_absorpt_empirical_full_min 0.799
_shelx_shelxl_version_number     2018/3
_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:
 C22(H22), C10(H10)
        2.b Aromatic/amide H refined with riding coordinates:
 C17(H17), C7(H7), C20(H20), C19(H19), C8(H8), C5(H5), C16(H16), C4(H4)
        2.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C23(H23A,H23B,H23C), C2(H2A,H2B,H2C), C24(H24A,H24B,
 H24C), C21(H21A,H21B,H21C), C9(H9A,H9B,H9C), C12(H12A,H12B,H12C), C11(H11A,
 H11B,H11C)
;
_shelx_res_checksum              83054