Mechanistic insights and comparative analysis of Ru(ii)–NNC pincer complexes with anionic-, protic-, and classical-NHCs for transfer hydrogenation of ketones
Nath, Shambhu; Yadav, Ekta; Raghuvanshi, Abhinav; Singh, Amrendra K.; Catalysis Science & Technology 13 (2023) 7085–7099; doi:10.1039/D3CY01383A

data_1570285
_publ_section_title
;
 Mechanistic insights and comparative analysis of Ru(ii)--NNC pincer
 complexes with anionic-, protic-, and classical-NHCs for transfer
 hydrogenation of ketones
;
_journal_issue                   24
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              7085
_journal_page_last               7099
_journal_paper_doi               10.1039/D3CY01383A
_journal_volume                  13
_journal_year                    2023
_chemical_formula_moiety         'C60 H49 Cl N5 O P2 Ru, Cl, C H4 O'
_chemical_formula_sum            'C61 H53 Cl2 N5 O2 P2 Ru'
_chemical_formula_weight         1121.99
_chemical_name_systematic        aks-sn-4-265
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-09-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-10-04 deposited with the CCDC.	2023-11-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 131.809(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.5479(11)
_cell_length_b                   22.1691(10)
_cell_length_c                   23.429(2)
_cell_measurement_reflns_used    5420
_cell_measurement_temperature    298
_cell_measurement_theta_max      70.4130
_cell_measurement_theta_min      4.3540
_cell_volume                     5245.0(13)
_computing_cell_refinement       'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      298
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0309
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.975
_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    -17.00  12.00   1.00   10.00    --    0.00  70.00  30.00   29
  2  \w     16.00  64.00   1.00   10.00    --    0.00  70.00  30.00   48
  3  \w     29.00 120.00   1.00   10.00    --   54.00  70.00  30.00   91
  4  \w    -15.00  78.00   1.00   10.00    --   54.00 -70.00-100.00   93
  5  \w     83.00 166.00   1.00   10.00    --  108.00  70.00  30.00   83
  6  \w     65.00 134.00   1.00   10.00    --  108.00 -70.00-100.00   69
  7  \w    -68.00  -3.00   1.00   10.00    --    0.00 -57.00 -60.00   65
  8  \w    -68.00 -34.00   1.00   10.00    --    0.00 -70.00-100.00   34
  9  \w     38.00 101.00   1.00   10.00    --   54.00  57.00 120.00   63
 10  \w    -11.00  15.00   1.00   10.00    --   54.00 -57.00 150.00   26
 11  \w     31.00 110.00   1.00   10.00    --   54.00-125.00  90.00   79
 12  \w     42.00  67.00   1.00   10.00    --   54.00 -57.00 150.00   25
 13  \w     40.00 112.00   1.00   10.00    --  108.00-111.00 -60.00   72
 14  \w    144.00 171.00   1.00   10.00    --  108.00  77.00 120.00   27
 15  \w     38.00 113.00   1.00   10.00    --  108.00-111.00  90.00   75
 16  \w     88.00 178.00   1.00   10.00    --  108.00  50.00  90.00   90
 17  \w     50.00  77.00   1.00   10.00    --  108.00-111.00 -90.00   27
 18  \w     36.00 101.00   1.00   10.00    --  108.00-111.00-180.00   65
 19  \w    101.00 159.00   1.00   10.00    --  108.00 111.00-150.00   58
 20  \w    117.00 176.00   1.00   10.00    --  108.00 111.00-120.00   59
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0939872000
_diffrn_orient_matrix_UB_12      0.0456604000
_diffrn_orient_matrix_UB_13      0.0648594000
_diffrn_orient_matrix_UB_21      -0.0193111000
_diffrn_orient_matrix_UB_22      -0.0321178000
_diffrn_orient_matrix_UB_23      0.0502416000
_diffrn_orient_matrix_UB_31      0.1186718000
_diffrn_orient_matrix_UB_32      -0.0413677000
_diffrn_orient_matrix_UB_33      0.0325212000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1173
_diffrn_reflns_av_unetI/netI     0.1304
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            25346
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.196
_diffrn_reflns_theta_min         3.904
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.327
_exptl_absorpt_correction_T_max  0.883
_exptl_absorpt_correction_T_min  0.775
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.95a (Rigaku Oxford Diffraction, 2021)
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            'metallic yellowish yellow'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.421
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2312
_exptl_crystal_preparation       'Ether/Methanol , v/v 1:1'
_exptl_crystal_recrystallization_method
'Slow deffusion of diethyl ether in methanol'
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.17
_refine_diff_density_max         1.757
_refine_diff_density_min         -2.007
_refine_diff_density_rms         0.121
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.116
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     661
_refine_ls_number_reflns         9922
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.116
_refine_ls_R_factor_all          0.1479
_refine_ls_R_factor_gt           0.0960
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2217
_refine_ls_wR_factor_ref         0.2727
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5656
_reflns_number_total             9922
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cy01383a2.cif
_cod_data_source_block           aks2
_cod_depositor_comments          'Adding full bibliography for 1570285.cif.'
_cod_original_cell_volume        5245.0(11)
_cod_database_code               1570285
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C61H53Cl2N5O2P2Ru
_shelx_estimated_absorpt_t_max   0.527
_shelx_estimated_absorpt_t_min   0.290
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 N1(H1), C00I(H00I), C00L(H00L), C00M(H00M), C00O(H00O), C00R(H00R),
 C00U(H00U), C00V(H00V), C00W(H00W), C00X(H00X), C00Y(H00Y), C00Z(H00Z),
 C010(H010), C011(H011), C012(H012), C013(H013), C014(H014), C015(H015),
 C017(H017), C018(H018), C019(H019), C01A(H01A), C01B(H01B), C01C(H01C),
 C01D(H01D), C01E(H01E), C01F(H01F), C01G(H01G), C01H(H01H), C01I(H01I),
 C01J(H01J), C01K(H01K), C01L(H01L), C01M(H01M), C01N(H01N), C01O(H01O),
 C01P(H01P), C01Q(H01Q), C01R(H01R), C01S(H01S), C01T(H01T), C01V(H01V),
 C01W(H01W), C01X(H01X), C01Y(H01Y), C01Z(H01Z)
2.b Idealised Me refined as rotating group:
 C020(H02D,H02E,H02F), C021(H02A,H02B,H02C)
2.c Idealised tetrahedral OH refined as rotating group:
 O00S(H00S)
;
_shelx_res_checksum              35930
_olex2_submission_original_sample_id AKS202A
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 7.674
_oxdiff_exptl_absorpt_empirical_full_min 0.314