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_7714110
_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         'C53 H52 N5 P2 Ru, Br0.175 Cl0.849, 1.5[H2O]'
_chemical_formula_sum            'C53 H55 Br0.17 Cl0.85 N5 O1.5 P2 Ru'
_chemical_formula_weight         993.11
_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
_audit_creation_date             2023-09-27
_audit_creation_method
;
Olex2 1.5
(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                 92.768(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.3216(2)
_cell_length_b                   26.5103(11)
_cell_length_c                   14.8679(3)
_cell_measurement_reflns_used    3962
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.8030
_cell_measurement_theta_min      4.7820
_cell_volume                     4850.9(2)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 16.0309
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.993
_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    -32.00   0.00   1.00    8.00    --    0.00 108.00  97.00   32
  2  \w     19.00  92.00   1.00    8.00    --   54.00-108.00   0.00   73
  3  \w     43.00 112.00   1.00    8.00    --  108.00-108.00   0.00   69
  4  \w    115.00 140.00   1.00    8.00    --  108.00 108.00  97.00   25
  5  \w    -64.00 -36.00   1.00    8.00    --    0.00 -57.00-120.00   28
  6  \w    -18.00  18.00   1.00    8.00    --    0.00  57.00 -60.00   36
  7  \w    -17.00  16.00   1.00    8.00    --    0.00 -57.00-120.00   33
  8  \w     35.00  60.00   1.00    8.00    --    0.00  57.00 -60.00   25
  9  \w     39.00 116.00   1.00    8.00    --   54.00  57.00-150.00   77
 10  \w     33.00 118.00   1.00    8.00    --   54.00  57.00 -60.00   85
 11  \w     -5.00  75.00   1.00    8.00    --   54.00 -57.00  30.00   80
 12  \w     35.00  61.00   1.00    8.00    --   54.00  57.00-180.00   26
 13  \w     23.00  49.00   1.00    8.00    --   54.00-125.00-180.00   26
 14  \w     86.00 169.00   1.00    8.00    --  108.00  63.00   0.00   83
 15  \w     77.00 138.00   1.00    8.00    --  108.00 -77.00   0.00   61
 16  \w    132.00 159.00   1.00    8.00    --  108.00  77.00 150.00   27
 17  \w     50.00  76.00   1.00    8.00    --  108.00 -77.00   0.00   26
 18  \w    105.00 162.00   1.00    8.00    --  108.00  38.00  90.00   57
 19  \w     42.00 103.00   1.00    8.00    --  108.00-111.00 -90.00   61
 20  \w     93.00 175.00   1.00    8.00    --  108.00  63.00 120.00   82
 21  \w    126.00 151.00   1.00    8.00    --  108.00 178.00 -60.00   25
 22  \w     41.00 108.00   1.00    8.00    --  108.00 -63.00 120.00   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  0.0843
_diffrn_reflns_av_unetI/netI     0.0851
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            21244
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.213
_diffrn_reflns_theta_min         3.411
_exptl_absorpt_coefficient_mu    4.184
_exptl_absorpt_correction_T_max  0.611
_exptl_absorpt_correction_T_min  0.456
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.360
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2058
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.16
_refine_diff_density_max         2.569
_refine_diff_density_min         -1.132
_refine_diff_density_rms         0.110
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     578
_refine_ls_number_reflns         8823
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0918
_refine_ls_R_factor_gt           0.0719
_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^)+(0.0961P)^2^+4.2621P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1823
_refine_ls_wR_factor_ref         0.2003
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6633
_reflns_number_total             8823
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03149g2.cif
_cod_data_source_block           aks214a9
_cod_original_formula_sum        'C53 H55 Br0.17 Cl0.85 N5 O1.50 P2 Ru'
_cod_database_code               7714110
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.554
_shelx_estimated_absorpt_t_min   0.398
_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:
 C12(H12), C15(H15)
2.b Aromatic/amide H refined with riding coordinates:
 C31(H31), C9(H9), C43(H43), C29(H29), C10(H10), C35(H35), C34(H34), C23(H23),
 C53(H53), C7(H7), C32(H32), C25(H25), C2(H2), C19(H19), C49(H49), C5(H5),
 C33(H33), C6(H6), C3(H3), C41(H41), C28(H28), C37(H37), C44(H44), C47(H47),
 C27(H27), C21(H21), C51(H51), C26(H26), C45(H45), C52(H52), C22(H22), C20(H20),
  C40(H40), C50(H50), C39(H39), C46(H46), C38(H38)
2.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C13(H13A,H13B,H13C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C)
;
_shelx_res_checksum              73995
_shelx_fab_checksum              44170
_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
;