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_1576683
_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         'C13 H22 Cl2 N2 Ru'
_chemical_formula_sum            'C13 H22 Cl2 N2 Ru'
_chemical_formula_weight         378.29
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_cell_setting           triclinic
_symmetry_Int_Tables_number      2
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-25T12:18:43-00:00
_audit_update_record
;
2025-09-11 deposited with the CCDC.	2025-12-29 downloaded from the CCDC.
;
_cell_angle_alpha                69.794(3)
_cell_angle_beta                 68.844(3)
_cell_angle_gamma                78.767(3)
_cell_formula_units_Z            2
_cell_length_a                   8.0151(3)
_cell_length_b                   10.3158(4)
_cell_length_c                   10.4456(3)
_cell_measurement_reflns_used    22849
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      80.101
_cell_measurement_theta_min      4.581
_cell_volume                     753.45(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (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 0.999
_diffrn_measured_fraction_theta_max 0.994
_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    -13.00  14.00   0.50    0.10    --   18.00 102.00-128.20   54
  2  \w      2.00  28.00   0.50    0.10    --   30.00  97.00-124.94   52
  3  \w      7.00  34.00   0.50    0.10    --   34.00  93.00 -50.28   54
  4  \w     -1.00  29.00   0.50    0.10    --   26.00  96.00  -8.65   60
  5  \w    -21.00   7.00   0.50    0.10    --   10.00 103.00  62.12   56
  6  \w     30.00 121.00   0.50    0.10    --   49.74  77.00  60.00  182
  7  \w     30.00 121.00   0.50    0.10    --   49.74  77.00 120.00  182
  8  \w     30.00 121.00   0.50    0.10    --   49.74  77.00 150.00  182
  9  \w     41.00 121.00   0.50    0.10    --   49.74  50.00  86.00  160
 10  \w     41.00 121.00   0.50    0.10    --   49.74  50.00  86.00  160
 11  \w     30.00 121.00   0.50    0.10    --   49.74  77.00-150.00  182
 12  \w    133.00 175.00   0.50    0.30    --  111.50  77.00  60.00   84
 13  \w    146.00 173.00   0.50    0.30    --  111.50  77.00 120.00   54
 14  \w    100.00 142.00   0.50    0.30    --  111.50  77.00 120.00   84
 15  \w     92.00 130.00   0.50    0.30    --  111.50  77.00  60.00   76
 16  \w     93.00 124.00   0.50    0.30    --  111.50  77.00  30.00   62
 17  \w    129.00 165.00   0.50    0.30    --  111.50  77.00  30.00   72
 18  \w    135.00 172.00   0.50    0.30    --  111.50  77.00   0.00   74
 19  \w     94.00 119.00   0.50    0.30    --  111.50  77.00   0.00   50
 20  \w     93.00 163.00   0.50    0.30    --  111.50  77.00  90.00  140
 21  \w     92.00 157.00   0.50    0.30    --  111.50  77.00 150.00  130
 22  \w     92.00 132.00   0.50    0.30    --  111.50  77.00 -90.00   80
 23  \w     93.00 148.00   0.50    0.30    --  111.50  77.00-150.00  110
 24  \w    100.00 166.00   0.50    0.30    --  111.50  77.00-180.00  132
 25  \w     97.00 177.00   0.50    0.30    --  111.50  77.00 -60.00  160
 26  \w     35.00 125.00   0.50    0.10    --   54.00  75.00   3.29  180
 27  \w     51.00  78.00   0.50    0.10    --   70.00  75.00 102.55   54
 28  \w     40.00  68.00   0.50    0.10    --   58.00  76.00 134.95   56
 29  \w     47.00  74.00   0.50    0.10    --   66.00  75.00 168.59   54
 30  \w    106.00 133.00   0.50    0.10    --   66.00  75.00 168.59   54
 31  \w     40.00  72.00   0.50    0.10    --   58.00  74.00  13.34   64
 32  \w     36.00 125.00   0.50    0.10    --   54.00  73.00 -16.36  178
 33  \w     36.00 125.00   0.50    0.10    --   54.00  73.00 -72.36  178
 34  \w     42.00  74.00   0.50    0.10    --   58.00  72.00-121.01   64
 35  \w     48.00  79.00   0.50    0.10    --   66.00  74.00-165.08   62
 36  \w     49.00  76.00   0.50    0.10    --   66.00  74.00 -76.22   54
 37  \w    101.00 130.00   0.50    0.30    --  111.50  61.00 -90.00   58
 38  \w    135.00 177.00   0.50    0.30    --  111.50  61.00 -90.00   84
 39  \w    103.00 174.00   0.50    0.30    --  111.50  61.00-120.00  142
 40  \w    104.00 152.00   0.50    0.30    --  111.50  61.00 -60.00   96
 41  \w    100.00 146.00   0.50    0.30    --  111.50  61.00  60.00   92
 42  \w    104.00 154.00   0.50    0.30    --  111.50  61.00 150.00  100
 43  \w    141.00 168.00   0.50    0.30    --  111.50  61.00 120.00   54
 44  \w     50.00  77.00   0.50    0.10    --   66.00  69.00  87.47   54
 45  \w     43.00  68.00   0.50    0.10    --   58.00  69.00  61.98   50
 46  \w    102.00 138.00   0.50    0.30    --  111.50  61.00 120.00   72
 47  \w    101.00 148.00   0.50    0.30    --  111.50  61.00  90.00   94
 48  \w    102.00 177.00   0.50    0.30    --  111.50  50.00  86.00  150
 49  \w    142.00 169.00   0.50    0.30    --  111.50  45.00  30.00   54
 50  \w    127.00 175.00   0.50    0.30    --  111.50  45.00   0.00   96
 51  \w    114.00 173.00   0.50    0.30    --  111.50  61.00 -30.00  118
 52  \w    104.00 148.00   0.50    0.30    --  111.50  45.00 -90.00   88
 53  \w    102.00 173.00   0.50    0.30    --  111.50  61.00-150.00  142
 54  \w    100.00 133.00   0.50    0.30    --  111.50  61.00-180.00   66
 55  \w     81.00 118.00   0.50    0.30    --  111.50   0.00 -90.00   74
 56  \w    -21.00  57.00   0.50    0.10    --   49.74 -50.00 -60.00  156
 57  \w     42.00  84.00   0.50    0.30    --  111.50 -77.00 -90.00   84
 58  \w     45.00 100.00   0.50    0.30    --  111.50 -77.00  90.00  110
 59  \w     41.00  83.00   0.50    0.30    --  111.50 -77.00 150.00   84
 60  \w     45.00  87.00   0.50    0.30    --  111.50 -77.00 120.00   84
 61  \w     41.00  68.00   0.50    0.30    --  111.50 -77.00  60.00   54
 62  \w     43.00  68.00   0.50    0.30    --  111.50 -61.00   0.00   50
 63  \w     78.00 103.00   0.50    0.30    --  111.50 -77.00   0.00   50
 64  \w     60.00  88.00   0.50    0.30    --  111.50 -77.00-180.00   56
 65  \w     41.00  69.00   0.50    0.30    --  111.50 -61.00-180.00   56
 66  \w     34.00  92.00   0.50    0.10    --   49.74-125.00-180.00  116
 67  \w     45.00 111.00   0.50    0.30    --  111.50-125.00 -90.00  132
 68  \w     46.00 109.00   0.50    0.30    --  111.50-125.00 -60.00  126
 69  \w     65.00 108.00   0.50    0.30    --  111.50-108.00-168.64   86
 70  \w     43.00 109.00   0.50    0.30    --  111.50-125.00   0.00  132
 71  \w     43.00  76.00   0.50    0.30    --  111.50-106.00  31.52   66
 72  \w     81.00 108.00   0.50    0.30    --  111.50-106.00  31.52   54
 73  \w     44.00  71.00   0.50    0.30    --  111.50-125.00 150.00   54
 74  \w     86.00 111.00   0.50    0.30    --  111.50-125.00 150.00   50
 75  \w     73.00 100.00   0.50    0.30    --  111.50 -94.00  90.00   54
 76  \w     69.00  96.00   0.50    0.30    --  111.50 -94.00  60.00   54
 77  \w     42.00  71.00   0.50    0.30    --  111.50 -94.00  90.00   58
 78  \w     60.00 101.00   0.50    0.30    --  111.50 -94.00   0.00   82
 79  \w     71.00 106.00   0.50    0.30    --  111.50 -94.00 -30.00   70
 80  \w     57.00 104.00   0.50    0.30    --  111.50 -94.00 -90.00   94
 81  \w     65.00  93.00   0.50    0.30    --  111.50 -94.00-180.00   56
 82  \w   -120.00 -30.00   0.50    0.10    --  -49.74 -77.00 120.00  180
 83  \w   -120.00 -30.00   0.50    0.10    --  -49.74 -77.00 120.00  180
 84  \w   -120.00 -40.00   0.50    0.10    --  -49.74 -50.00 -60.00  160
 85  \w   -120.00 -40.00   0.50    0.10    --  -49.74 -50.00 -60.00  160
 86  \w   -120.00 -30.00   0.50    0.10    --  -49.74 -77.00 -90.00  180
 87  \w   -120.00 -30.00   0.50    0.10    --  -49.74 -77.00 -90.00  180
 88  \w   -121.00 -46.00   0.50    0.10    --  -49.74 -26.00  11.24  150
 89  \w   -121.00 -46.00   0.50    0.10    --  -49.74 -26.00  11.24  150
 90  \w   -121.00 -45.00   0.50    0.10    --  -49.74 -19.00-180.00  152
 91  \w   -121.00 -45.00   0.50    0.10    --  -49.74 -19.00-180.00  152
 92  \w   -104.00 -77.00   0.50    0.30    --  -90.00 -77.00-120.00   54
 93  \w    -97.00 -70.00   0.50    0.30    --  -90.00 -77.00-150.00   54
 94  \w   -161.00-123.00   0.50    0.30    --  -90.00 -77.00-150.00   76
 95  \w   -159.00-132.00   0.50    0.30    --  -90.00 -77.00-120.00   54
 96  \w   -143.00-116.00   0.50    0.30    --  -90.00 -77.00 -60.00   54
 97  \w    -97.00 -71.00   0.50    0.30    --  -90.00 -75.00-107.83   52
 98  \w    -97.00 -70.00   0.50    0.30    --  -90.00 -77.00 -60.00   54
 99  \w   -113.00 -72.00   0.50    0.30    --  -90.00 -74.00  44.51   82
100  \w   -117.00 -72.00   0.50    0.30    --  -90.00 -73.00  16.98   90
101  \w   -152.00-125.00   0.50    0.30    --  -90.00 -74.00  44.51   54
102  \w    -97.00 -70.00   0.50    0.30    --  -90.00 -77.00 150.00   54
103  \w    -85.00 -60.00   0.50    0.10    --  -78.00 -72.00 115.99   50
104  \w   -117.00 -70.00   0.50    0.30    --  -90.00 -77.00 120.00   94
105  \w    -86.00 -60.00   0.50    0.10    --  -78.00 -72.00  17.62   52
106  \w   -103.00 -73.00   0.50    0.30    --  -90.00 -72.00 -10.79   60
107  \w   -109.00 -72.00   0.50    0.30    --  -90.00 -72.00  89.09   74
108  \w   -160.00-110.00   0.50    0.30    --  -90.00 -72.00 -10.79  100
109  \w    -96.00 -69.00   0.50    0.30    --  -86.00 -71.00  61.61   54
110  \w    -85.00 -58.00   0.50    0.10    --  -74.00 -71.00  56.35   54
111  \w    -91.00 -65.00   0.50    0.30    --  -82.00 -71.00 -12.13   52
112  \w    -99.00 -72.00   0.50    0.30    --  -90.00 -72.00 -35.77   54
113  \w   -101.00 -74.00   0.50    0.30    --  -90.00 -67.00 -56.05   54
114  \w    -99.00 -72.00   0.50    0.30    --  -90.00 -72.00 -85.83   54
115  \w    -82.00 -55.00   0.50    0.10    --  -70.00 -66.00-154.99   54
116  \w    -83.00 -56.00   0.50    0.10    --  -74.00 -73.00-176.10   54
117  \w   -107.00 -80.00   0.50    0.30    --  -90.00 -65.00-178.09   54
118  \w   -150.00-123.00   0.50    0.30    --  -90.00 -67.00 -56.05   54
119  \w    -88.00 -61.00   0.50    0.10    --  -74.00 -63.00-131.75   54
120  \w    -90.00 -64.00   0.50    0.10    --  -78.00 -64.00 -49.95   52
121  \w    -83.00 -53.00   0.50    0.10    --  -66.00 -62.00 -52.60   60
122  \w   -100.00 -69.00   0.50    0.30    --  -82.00 -65.00  -9.55   62
123  \w    -93.00 -61.00   0.50    0.10    --  -74.00 -60.00 -74.02   64
124  \w    -87.00 -52.00   0.50    0.10    --  -66.00 -65.00  13.15   70
125  \w    -95.00 -68.00   0.50    0.30    --  -82.00 -64.00  81.00   54
126  \w    -90.00 -63.00   0.50    0.10    --  -74.00 -62.00 113.68   54
127  \w    -89.00 -63.00   0.50    0.10    --  -74.00 -56.00 113.44   52
128  \w   -100.00 -73.00   0.50    0.30    --  -82.00 -59.00 152.28   54
129  \w    -84.00 -57.00   0.50    0.10    --  -66.00 -57.00  66.12   54
130  \w   -105.00 -78.00   0.50    0.30    --  -90.00 -57.00-162.57   54
131  \w   -161.00 -81.00   0.50    0.30    --  -90.00 -50.00 -60.00  160
132  \w    -48.00 -20.00   0.50    0.30    --  -90.00  45.00 -60.00   56
133  \w    -60.00  22.00   0.50    0.10    --  -30.00 100.00  69.32  164
134  \w    -57.00  22.00   0.50    0.10    --  -49.74  50.00  86.00  158
135  \w    -57.00 -18.00   0.50    0.30    --  -90.00  50.00  86.00   78
136  \w    -70.00 -19.00   0.50    0.30    --  -90.00  61.00-180.00  102
;
_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      -0.1560099
_diffrn_orient_matrix_UB_12      0.0952801
_diffrn_orient_matrix_UB_13      -0.044709
_diffrn_orient_matrix_UB_21      0.1114026
_diffrn_orient_matrix_UB_22      0.0219147
_diffrn_orient_matrix_UB_23      -0.1596709
_diffrn_orient_matrix_UB_31      -0.0774718
_diffrn_orient_matrix_UB_32      -0.12621
_diffrn_orient_matrix_UB_33      0.0016037
_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  0.0452
_diffrn_reflns_av_unetI/netI     0.0169
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            30311
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.502
_diffrn_reflns_theta_min         4.582
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.549
_exptl_absorpt_correction_T_max  0.483
_exptl_absorpt_correction_T_min  0.273
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
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            red
_exptl_crystal_density_diffrn    1.667
_exptl_crystal_description       irregular
_exptl_crystal_F_000             384
_exptl_crystal_size_max          0.169
_exptl_crystal_size_mid          0.124
_exptl_crystal_size_min          0.085
_refine_diff_density_max         1
_refine_diff_density_min         -0.876
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     176
_refine_ls_number_reflns         3054
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0272
_refine_ls_R_factor_gt           0.0269
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0495P)^2^+0.4115P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0721
_refine_ls_wR_factor_ref         0.0724
_reflns_Friedel_coverage         0
_reflns_number_gt                3003
_reflns_number_total             3054
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08206d2.cif
_cod_data_source_block           Ru-6
_cod_depositor_comments
'Adding full bibliography for 1576683--1576688.cif.'
_cod_original_cell_volume        753.44(5)
_cod_database_code               1576683
_shelx_estimated_absorpt_t_min   0.244
_shelx_estimated_absorpt_t_max   0.458
_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 1.766
_oxdiff_exptl_absorpt_empirical_full_min 0.565
_shelx_shelxl_version_number     2019/3
_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:
 C11(H11)
        2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C5(H5), C6(H6)
        2.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C12(H12A,H12B,H12C), C10(H10A,H10B,H10C),
 C13(H13A,H13B,H13C)
;
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