Efficient hydrogenation of ketones and aldehydes catalysed by a well-defined PNNP-rhenium complex.
Xu, Shuting; Zhang, Yu; Li, Bin; Li, Hao; Huang, Jing; Chen, Yiyu; Hu, Kun; Zhang, Fengjun; Fang, Xiaolong; Dalton transactions (Cambridge, England : 2003) 54 (2025) 10396–10402; doi:10.1039/d5dt01368b

data_7718872
_publ_section_title
;
 Efficient hydrogenation of ketones and aldehydes catalysed by a
 well-defined PNNP-rhenium complex.
;
_journal_issue                   26
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10396
_journal_page_last               10402
_journal_paper_doi               10.1039/d5dt01368b
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety
'C42 H38 N2 O2 P2 Re, Cl, 1.5(C2 H6 O), 0.25[C2H6O]'
_chemical_formula_sum            'C45.5 H48.5 Cl N2 O3.75 P2 Re'
_chemical_formula_weight         966.95
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-06-04
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-06-09 deposited with the CCDC.	2025-06-11 downloaded from the CCDC.
;
_cell_angle_alpha                75.1370(10)
_cell_angle_beta                 81.8350(10)
_cell_angle_gamma                67.072(2)
_cell_formula_units_Z            4
_cell_length_a                   12.5495(2)
_cell_length_b                   15.2226(3)
_cell_length_c                   24.5566(2)
_cell_measurement_reflns_used    36637
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      77.8270
_cell_measurement_theta_min      3.2170
_cell_volume                     4171.34(13)
_computing_cell_refinement       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_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_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.960
_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     41.00  78.00   0.50    0.25    --   49.58-125.00  30.00   74
  2  \w     24.00  51.00   0.50    0.25    --   49.58-125.00  90.00   54
  3  \w     59.00  86.00   0.50    0.25    --   49.58-125.00  90.00   54
  4  \w     37.00  69.00   0.50    0.80    --  106.85 -57.00   0.00   64
  5  \w     44.00  69.00   0.50    0.80    --  106.85 -57.00 -30.00   50
  6  \w     49.00 105.00   0.50    0.80    --  106.85 -99.00   0.00  112
  7  \w     80.00 106.00   0.50    0.80    --  106.85-104.00  -5.16   52
  8  \w     53.00  83.00   0.50    0.80    --  106.85-125.00 -60.00   60
  9  \w     38.00 101.00   0.50    0.80    --  106.85-104.00 -91.78  126
 10  \w     60.00 104.00   0.50    0.80    --  106.85 -99.00-180.00   88
 11  \w     40.00 101.00   0.50    0.80    --  106.85 -99.00-150.00  122
 12  \w     38.00  63.00   0.50    0.80    --  106.85-104.00  -5.16   50
 13  \w     37.00 105.00   0.50    0.80    --  106.85 -99.00 -60.00  136
 14  \w     50.00 108.00   0.50    0.80    --  106.85-107.00  65.78  116
 15  \w     79.00 106.00   0.50    0.80    --  106.85 -99.00  60.00   54
 16  \w     41.00  89.00   0.50    0.80    --  106.85 -99.00  90.00   96
 17  \w     47.00 103.00   0.50    0.80    --  106.85 -99.00 120.00  112
 18  \w     43.00 104.00   0.50    0.80    --  106.85 -99.00 150.00  122
 19  \w    -23.00  26.00   0.50    0.25    --   49.58 -19.00  60.00   98
 20  \w     12.00  47.00   0.50    0.25    --   49.58 -38.00-180.00   70
 21  \w      7.00  33.00   0.50    0.25    --   49.58 -25.00-166.00   52
 22  \w      3.00  68.00   0.50    0.25    --   49.58 -77.00-180.00  130
 23  \w   -169.00-100.00   0.50    0.80    -- -104.50 -25.00-166.00  138
 24  \w   -162.00-136.00   0.50    0.80    -- -104.50 -99.00 -90.00   52
 25  \w   -111.00 -86.00   0.50    0.80    -- -104.50 -99.00 -90.00   50
 26  \w   -123.00 -49.00   0.50    0.25    --  -49.58 -25.00-166.00  148
 27  \w    -63.00 -35.00   0.50    0.80    -- -104.50 125.00 120.00   56
 28  \w   -121.00 -95.00   0.50    0.80    -- -104.50 137.00-118.08   52
 29  \w    -58.00 -32.00   0.50    0.80    -- -104.50  77.00-120.00   52
 30  \w    -62.00 -34.00   0.50    0.80    -- -104.50  57.00-150.00   56
 31  \w    -62.00 -37.00   0.50    0.80    -- -104.50  57.00  30.00   50
 32  \w    -58.00 -33.00   0.50    0.80    -- -104.50  57.00  90.00   50
 33  \w    -62.00 -33.00   0.50    0.80    -- -104.50  57.00 150.00   58
 34  \w    -62.00 -32.00   0.50    0.80    -- -104.50  57.00 120.00   60
 35  \w    -60.00 -32.00   0.50    0.80    -- -104.50  57.00   0.00   56
 36  \w    -62.00 -34.00   0.50    0.80    -- -104.50  57.00-180.00   56
 37  \w    -62.00 -36.00   0.50    0.25    --  -49.58  57.00-180.00   52
 38  \w    -14.00  21.00   0.50    0.25    --  -49.58  57.00-180.00   70
 39  \w    -10.00  16.00   0.50    0.25    --  -49.58  25.00  -2.00   52
 40  \w     42.00 123.00   0.50    0.25    --   49.58  25.00  -2.00  162
 41  \w    118.00 177.00   0.50    0.80    --  106.85  25.00  -2.00  118
 42  \w    135.00 162.00   0.50    0.80    --  106.85  57.00 -60.00   54
 43  \w    103.00 128.00   0.50    0.80    --  106.85  57.00 -60.00   50
 44  \w     88.00 151.00   0.50    0.80    --  106.85  77.00-150.00  126
 45  \w    106.00 176.00   0.50    0.80    --  106.85  19.00 -90.00  140
 46  \w    115.00 177.00   0.50    0.80    --  106.85  19.00 -60.00  124
 47  \w     38.00 149.00   0.50    0.80    --  106.85   0.00 150.00  222
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1213224000
_diffrn_orient_matrix_UB_12      0.0015683000
_diffrn_orient_matrix_UB_13      0.0021547000
_diffrn_orient_matrix_UB_21      0.0549216000
_diffrn_orient_matrix_UB_22      -0.0953266000
_diffrn_orient_matrix_UB_23      -0.0215861000
_diffrn_orient_matrix_UB_31      -0.0083929000
_diffrn_orient_matrix_UB_32      0.0600241000
_diffrn_orient_matrix_UB_33      -0.0612514000
_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  0.0655
_diffrn_reflns_av_unetI/netI     0.0465
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            54583
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.376
_diffrn_reflns_theta_min         3.232
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.365
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44866
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.540
_exptl_crystal_description       block
_exptl_crystal_F_000             1950
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         2.697
_refine_diff_density_min         -3.084
_refine_diff_density_rms         0.197
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     988
_refine_ls_number_reflns         17199
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0531
_refine_ls_R_factor_gt           0.0504
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1139P)^2^+0.5645P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1439
_refine_ls_wR_factor_ref         0.1463
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15835
_reflns_number_total             17199
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01368b2.cif
_cod_data_source_block           exp_66_auto
_cod_depositor_comments
'Adding full bibliography for 7718872--7718874.cif.'
_cod_original_formula_sum        'C45.50 H48.50 Cl N2 O3.75 P2 Re'
_cod_database_code               7718872
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.590
_shelx_estimated_absorpt_t_min   0.405
_diffrn_oxdiff_digest_hkl
;
01b2afd8c870075992b9e4c2bccba6ac11cc7b
;
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 H1-H00G
 2.4 with sigma of 0.01
3.a Ternary CH refined with riding coordinates:
 N2(H2), N4(H4), N1(H1), N3(H3)
3.b Secondary CH2 refined with riding coordinates:
 C00S(H00A,H00B), C011(H01A,H01B), C01J(H01M,H01O), C01M(H01Q,H01T), C01T(H01C,
 H01D), C01Y(H01,H), C022(H02D,H02I), C025(H02A,H02B), C02A(H02Z,HA), C030(H03A,
 H03B), C5(H5B,H5C)
3.c Aromatic/amide H refined with riding coordinates:
 C00O(H00O), C00T(H00T), C00U(H00U), C00V(H00V), C010(H010), C013(H013),
 C015(H015), C016(H016), C017(H017), C018(H018), C019(H019), C01A(H01E),
 C01D(H01G), C01F(H01F), C01G(H01I), C01H(H01H), C01I(H01J), C01K(H01K),
 C01L(H01L), C01N(H01N), C01O(H01U), C01P(H01P), C01Q(H01W), C01R(H01R),
 C01S(H01S), C01U(H01Y), C01V(H01V), C01X(H01X), C01Z(H01Z), C021(H021),
 C023(H023), C024(H024), C026(H026), C028(H028), C029(H029), C02B(H02J),
 C02C(H02C), C02D(H02K), C02E(H02E), C02F(H02F), C02G(H02G), C02H(H02H),
 C02I(H02L), C02K(H02M), C02L(H02O), C02N(H02N), C02O(H02P), C02P(H02S),
 C02Q(H02Q), C02R(H02R), C02S(H02T), C02T(H02U), C02U(H02V), C02V(H02W),
 C02W(H02X), C02X(H02Y)
3.d Idealised Me refined as rotating group:
 C02M(H02,HB,HC), C02Y(H5,HD,HE), C6(H6A,H6B,H6C)
3.e Idealised tetrahedral OH refined as rotating group:
 O00B(H00C), O00G(H00G), O5(H5A)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              1335
_shelx_hkl_checksum              30329
_shelx_fab_checksum              13787
_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 5.184
_oxdiff_exptl_absorpt_empirical_full_min 0.245