Role of Ancillary Ligands in Selectivity Towards Acceptorless Dehydrogenation versus Dehydrogenative Coupling of Alcohols and Amines Catalyzed by Cationic Ruthenium(II)-CNC Pincer Complexes
Singh, Rahul Kumar; Yadav, Dibya; Misra, Shilpi; Singh, Amrendra Kumar; Dalton Transactions  (2023) –; doi:10.1039/D3DT03149G

data_7714111
_publ_section_title
;
 Role of Ancillary Ligands in Selectivity Towards Acceptorless
 Dehydrogenation versus Dehydrogenative Coupling of Alcohols and Amines
 Catalyzed by Cationic Ruthenium(II)-CNC Pincer Complexes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT03149G
_journal_year                    2023
_chemical_formula_moiety         'C21 H33 Cl N5 O2 Ru S2, Cl, 3(H2 O)'
_chemical_formula_sum            'C21 H39 Cl2 N5 O5 Ru S2'
_chemical_formula_weight         677.66
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-09-28
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-10-03 deposited with the CCDC.	2023-10-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.679(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.3804(2)
_cell_length_b                   11.0157(2)
_cell_length_c                   24.3528(4)
_cell_measurement_reflns_used    8346
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.9160
_cell_measurement_theta_min      4.5210
_cell_volume                     3032.22(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 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5-beta (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 16.0309
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_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    -73.00 -48.00   1.00   10.00    --    0.00 161.00-157.00   25
  2  \w    -49.00   5.00   1.00   10.00    --    0.00 117.00  50.00   54
  3  \w     91.00 117.00   1.00   10.00    --   54.00 161.00-157.00   26
  4  \w     86.00 111.00   1.00   10.00    --   54.00-161.00 172.00   25
  5  \w     37.00  62.00   1.00   10.00    --   54.00-117.00 -36.00   25
  6  \w     92.00 117.00   1.00   10.00    --  108.00 161.00-157.00   25
  7  \w     99.00 125.00   1.00   10.00    --  108.00 117.00  50.00   26
  8  \w     72.00 138.00   1.00   10.00    --  108.00-161.00 172.00   66
  9  \w     36.00 113.00   1.00   10.00    --  108.00-117.00 -36.00   77
 10  \w     -5.00  62.00   1.00   10.00    --    0.00  57.00 -90.00   67
 11  \w     37.00  63.00   1.00   10.00    --    0.00  57.00-180.00   26
 12  \w     40.00 116.00   1.00   10.00    --   54.00  57.00   0.00   76
 13  \w      3.00  96.00   1.00   10.00    --   54.00 -99.00 -60.00   93
 14  \w     73.00  98.00   1.00   10.00    --   54.00  77.00-150.00   25
 15  \w     30.00 119.00   1.00   10.00    --   54.00  38.00  90.00   89
 16  \w     89.00 137.00   1.00   10.00    --  108.00 -77.00 -60.00   48
 17  \w     39.00  65.00   1.00   10.00    --  108.00 -77.00 -60.00   26
 18  \w     85.00 147.00   1.00   10.00    --  108.00 178.00 -30.00   62
 19  \w     36.00  78.00   1.00   10.00    --  108.00-111.00-150.00   42
 20  \w     86.00 170.00   1.00   10.00    --  108.00  63.00  90.00   84
 21  \w     86.00 178.00   1.00   10.00    --  108.00  50.00-150.00   92
 22  \w     49.00 116.00   1.00   10.00    --  108.00 -50.00  90.00   67
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0897
_diffrn_reflns_av_unetI/netI     0.0543
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            13368
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.246
_diffrn_reflns_theta_min         3.655
_exptl_absorpt_coefficient_mu    7.416
_exptl_absorpt_correction_T_max  0.780
_exptl_absorpt_correction_T_min  0.673
_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    1.484
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1400
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.18
_refine_diff_density_max         2.419
_refine_diff_density_min         -0.911
_refine_diff_density_rms         0.143
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     342
_refine_ls_number_reflns         5531
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0909
_refine_ls_R_factor_gt           0.0866
_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^)+(0.1911P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2388
_refine_ls_wR_factor_ref         0.2488
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4783
_reflns_number_total             5531
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03149g2.cif
_cod_data_source_block           aks171a8
_cod_database_code               7714111
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.349
_shelx_estimated_absorpt_t_min   0.207
_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,H) groups
2.a Free rotating group:
 O3S(H3SA,H3SB), O2S(H2SA,H2SB), O1S(H1SA,H1SB)
2.b Ternary CH refined with riding coordinates:
 C15(H15), C12(H12)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C9(H9), C3(H3), C10(H10), C6(H6), C5(H5), C7(H7)
2.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C21(H21A,H21B,H21C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C20(H20A,
 H20B,H20C)
;
_shelx_res_checksum              53046
_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
- B-factor correction
;