Non-bifunctional Mn catalysts based on phosphine–phosphites for the hydrogenation of carbonyl substrates
Jiménez, Verónica; González, Carmen; Serrano, Joaquín López; Fernández de Córdova, Francisco; Pizzano, Antonio; Catalysis Science & Technology 15 (2025) 6666–6677; doi:10.1039/D5CY00906E

data_1575841
_publ_section_title
;
 Non-bifunctional Mn catalysts based on phosphine--phosphites for the
 hydrogenation of carbonyl substrates
;
_journal_issue                   22
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              6666
_journal_page_last               6677
_journal_paper_doi               10.1039/D5CY00906E
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety         'C49 H54 Br Mn O6 P2'
_chemical_formula_sum            'C49 H54 Br Mn O6 P2'
_chemical_formula_weight         935.71
_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             2025-09-02
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-09-03 deposited with the CCDC.	2025-09-22 downloaded from the CCDC.
;
_cell_angle_alpha                79.160(2)
_cell_angle_beta                 85.944(2)
_cell_angle_gamma                80.855(2)
_cell_formula_units_Z            2
_cell_length_a                   9.3612(4)
_cell_length_b                   10.4559(4)
_cell_length_c                   24.2055(10)
_cell_measurement_reflns_used    9923
_cell_measurement_temperature    193.00
_cell_measurement_theta_max      28.250
_cell_measurement_theta_min      2.205
_cell_volume                     2295.34(16)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Apex5 v2023.9-2 (Bruker, 2023)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      193.00
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0799
_diffrn_reflns_av_unetI/netI     0.0349
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            125244
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.339
_diffrn_reflns_theta_min         2.005
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.275
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6821
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0991 before and 0.0663 after correction.
The Ratio of minimum to maximum transmission is 0.9147.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.354
_exptl_crystal_description       plate
_exptl_crystal_F_000             972
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CH2Cl2'
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.393
_refine_diff_density_min         -0.361
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     572
_refine_ls_number_reflns         11398
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0547
_refine_ls_R_factor_gt           0.0343
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0281P)^2^+1.4712P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0717
_refine_ls_wR_factor_ref         0.0816
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9017
_reflns_number_total             11398
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy00906e3.cif
_cod_data_source_block           apm0123a_0m
_cod_depositor_comments          'Adding full bibliography for 1575841.cif.'
_cod_database_code               1575841
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.842
_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. Restrained distances
 Mn1-C3 \\sim Mn1-C3A
 with sigma of 0.02
 Mn1-O3 \\sim Mn1-O3A
 with sigma of 0.04
3. Rigid bond restraints
 O3A, C3A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Mn1 \\sim O3A \\sim C3A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
5. Others
 Sof(Br1A)=Sof(O3A)=Sof(C3A)=1-FVAR(1)
 Sof(Br1)=Sof(O3)=Sof(C3)=FVAR(1)
6.a Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15), C17(H17), C18(H18), C19(H19), C20(H20), C24(H24), C26(H26),
  C39(H39), C41(H41)
6.b Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C33(H33A,H33B,
 H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C43(H43C,H43A,H43B), C44(H44B,
 H44C,H44A), C45(H45A,H45B,H45C), C47(H47B,H47C,H47A), C48(H48C,H48A,H48B),
 C49(H49A,H49C,H49B)
;
_shelx_res_checksum              46488
_olex2_submission_special_instructions 'No special instructions were received'