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_1576687
_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         'C16 H26 Cl2 N2 Ru'
_chemical_formula_sum            'C16 H26 Cl2 N2 Ru'
_chemical_formula_weight         418.36
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      61
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-25T12:32:29-00:00
_audit_update_record
;
2025-09-11 deposited with the CCDC.	2025-12-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.43884(6)
_cell_length_b                   15.36310(9)
_cell_length_c                   19.58592(10)
_cell_measurement_reflns_used    29459
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      80.202
_cell_measurement_theta_min      4.512
_cell_volume                     3441.95(3)
_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 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    119.00 172.00   0.50    0.40    --  111.50 125.00-120.00  106
  2  \w    -22.00  31.00   0.50    0.30    --   49.99 -25.00 127.00  106
  3  \w    -22.00  26.00   0.50    0.30    --   49.99 -19.00   0.00   96
  4  \w     43.00 111.00   0.50    0.40    --  111.50-125.00-120.00  136
  5  \w     63.00  94.00   0.50    0.40    --  111.50-125.00 -90.00   62
  6  \w     81.00 109.00   0.50    0.40    --  111.50-125.00  60.00   56
  7  \w     44.00  76.00   0.50    0.40    --  111.50-125.00  60.00   64
  8  \w     55.00 103.00   0.50    0.40    --  111.50 -94.00  60.00   96
  9  \w     41.00 106.00   0.50    0.40    --  111.50 -94.00  30.00  130
 10  \w     60.00  86.00   0.50    0.40    --  111.50 -94.00   0.00   52
 11  \w     57.00 102.00   0.50    0.40    --  111.50 -77.00 -60.00   90
 12  \w     41.00 104.00   0.50    0.40    --  111.50 -77.00-120.00  126
 13  \w     43.00  68.00   0.50    0.40    --  111.50 -61.00  30.00   50
 14  \w     42.00  69.00   0.50    0.40    --  111.50 -61.00  60.00   54
 15  \w     44.00  70.00   0.50    0.40    --  111.50 -61.00 120.00   52
 16  \w     64.00 105.00   0.50    0.40    --  111.50 -77.00 120.00   82
 17  \w     45.00  70.00   0.50    0.40    --  111.50 -61.00 -30.00   50
 18  \w     41.00  69.00   0.50    0.40    --  111.50 -61.00 -90.00   56
 19  \w     41.00  71.00   0.50    0.40    --  111.50 -61.00-120.00   60
 20  \w    148.00 174.00   0.50    0.40    --  111.50  45.00-120.00   52
 21  \w    113.00 139.00   0.50    0.40    --  111.50  45.00-120.00   52
 22  \w    108.00 177.00   0.50    0.40    --  111.50  25.00 -68.00  138
 23  \w    110.00 172.00   0.50    0.40    --  111.50  30.00 120.00  124
 24  \w     63.00 118.00   0.50    0.40    --  111.50   0.00 150.00  110
 25  \w     63.00 118.00   0.50    0.40    --  111.50   0.00  60.00  110
 26  \w     46.00 123.00   0.50    0.30    --   49.99  25.00 -68.00  154
 27  \w    -26.00  22.00   0.50    0.30    --  -49.99  19.00  60.00   96
 28  \w    -31.00  23.00   0.50    0.30    --  -49.99  25.00 -68.00  108
 29  \w    -51.00 -18.00   0.50    0.40    --  -90.00  45.00 -90.00   66
 30  \w    -85.00 -21.00   0.50    0.40    --  -90.00 125.00   0.00  128
 31  \w   -122.00 -46.00   0.50    0.30    --  -49.99 -25.00 127.00  152
 32  \w   -162.00 -85.00   0.50    0.40    --  -90.00 -25.00 127.00  154
 33  \w   -119.00 -73.00   0.50    0.30    --  -49.99-125.00-150.00   92
;
_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      0.1099905
_diffrn_orient_matrix_UB_12      -0.0504901
_diffrn_orient_matrix_UB_13      -0.0221977
_diffrn_orient_matrix_UB_21      -0.0750203
_diffrn_orient_matrix_UB_22      -0.0817715
_diffrn_orient_matrix_UB_23      -0.0122902
_diffrn_orient_matrix_UB_31      -0.0203834
_diffrn_orient_matrix_UB_32      0.0285557
_diffrn_orient_matrix_UB_33      -0.0744617
_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  0.0243
_diffrn_reflns_av_unetI/netI     0.0119
_diffrn_reflns_Laue_measured_fraction_full 1
_diffrn_reflns_Laue_measured_fraction_max 1
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            34841
_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         74.49
_diffrn_reflns_theta_min         4.515
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.176
_exptl_absorpt_correction_T_max  0.964
_exptl_absorpt_correction_T_min  0.076
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
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            orange
_exptl_crystal_density_diffrn    1.615
_exptl_crystal_description       block
_exptl_crystal_F_000             1712
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.444
_refine_diff_density_min         -0.372
_refine_diff_density_rms         0.059
_refine_ls_extinction_coef       0.000294(15)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.101
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     199
_refine_ls_number_reflns         3516
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.101
_refine_ls_R_factor_all          0.0189
_refine_ls_R_factor_gt           0.0187
_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^)+(0.0203P)^2^+2.7262P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0461
_refine_ls_wR_factor_ref         0.0462
_reflns_Friedel_coverage         0
_reflns_number_gt                3478
_reflns_number_total             3516
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08206d2.cif
_cod_data_source_block           Ru-2c
_cod_depositor_comments
'Adding full bibliography for 1576683--1576688.cif.'
_cod_database_code               1576687
_shelx_estimated_absorpt_t_min   0.106
_shelx_estimated_absorpt_t_max   0.63
_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 0.842
_shelx_shelxl_version_number     2019/3
_olex2_refinement_description
;
        1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
        2.a Ternary CH refined with riding coordinates:
 C14(H14)
        2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C5(H5A,H5B), C4(H4A,H4B), C3(H3A,H3B)
        2.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C8(H8), C9(H9), C11(H11)
        2.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C13(H13A,H13B,H13C), C6(H6A,H6B,H6C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              43342