Catalyst speciation and deactivation in the ruthenium-mediated transformation of ethynyl-β-ionol to α,β-unsaturated esters for vitamin A synthesis
Saib, Asad; Goy, Roman; Medlock, Jonathan; Wüstenberg, Bettina; Kociok-Köhn, Gabriele; Lyall, Catherine L.; Lowe, John P.; Hintermair, Ulrich; Catalysis Science & Technology 15 (2025) 355–375; doi:10.1039/D4CY01032A

data_1573249
_publ_section_title
;
 Catalyst speciation and deactivation in the ruthenium-mediated
 transformation of ethynyl-\b-ionol to \a,\b-unsaturated esters for
 vitamin A synthesis
;
_journal_issue                   2
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              355
_journal_page_last               375
_journal_paper_doi               10.1039/D4CY01032A
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety         'C96 H108 O9 P4 Ru2, C3 H6 O [+ solvent]'
_chemical_formula_sum            'C99 H114 O10 P4 Ru2'
_chemical_formula_weight         1789.92
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_method           SHELXL-2018/3
_audit_update_record
;
2023-09-20 deposited with the CCDC.	2024-11-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.926(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.8453(3)
_cell_length_b                   24.5721(4)
_cell_length_c                   29.3748(6)
_cell_measurement_reflns_used    67964
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      72.7400
_cell_measurement_theta_min      4.3090
_cell_volume                     9777.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics
'ORTEP3 for Windows - Farrugia, L. J. J. Appl. Crystallogr. 1997, 30, 565'
_computing_publication_material
;
 'WinGX publication routines, Farrugia, 
 L. J., J. Appl. Crystallogr., 1999, 32, 837-838
;
_computing_structure_refinement
;
 SHELXL-2018/3 (Sheldrick, 2018)
 Sheldrick GM (2008) Acta Crystallogr A64:112--122 and 
 C. B. H\"ubschle, G. M. Sheldrick and B. Dittrich
 ShelXle: a Qt graphical user interface for SHELXL
 J. Appl. Cryst., 44, (2011) 1281-1284.
;
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1150
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.1139
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            197376
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.247
_diffrn_reflns_theta_min         3.598
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.540
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.442
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.56a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.216
_exptl_crystal_description       needle
_exptl_crystal_F_000             3744
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetone, MeOH'
_exptl_crystal_size_max          0.339
_exptl_crystal_size_mid          0.059
_exptl_crystal_size_min          0.033
_refine_diff_density_max         1.639
_refine_diff_density_min         -2.019
_refine_diff_density_rms         0.198
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.131
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1065
_refine_ls_number_reflns         197376
_refine_ls_number_restraints     102
_refine_ls_restrained_S_all      1.133
_refine_ls_R_factor_all          0.1223
_refine_ls_R_factor_gt           0.1016
_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^)+(0.0074P)^2^+131.5198P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2199
_refine_ls_wR_factor_ref         0.2299
_reflns_Friedel_coverage         0.000
_reflns_number_gt                155650
_reflns_number_total             197376
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cy01032a2.cif
_cod_data_source_block           s22uh10_sq
_cod_depositor_comments
'Adding full bibliography for 1573241--1573249.cif.'
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               1573249
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.380
_shelx_estimated_absorpt_t_max   0.892
_oxdiff_exptl_absorpt_empirical_full_min 0.359
_oxdiff_exptl_absorpt_empirical_full_max 1.451
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_shelx_res_checksum              80772
_shelx_fab_checksum              71003