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_1573248
_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         '4(C80 H68 O9 P4 Ru2), 0.5(C6 H14), 5(C3 H6 O)'
_chemical_formula_sum            'C338 H309 O41 P16 Ru8'
_chemical_formula_weight         6330.91
_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
_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                88.9659(18)
_cell_angle_beta                 76.443(2)
_cell_angle_gamma                76.138(2)
_cell_formula_units_Z            1
_cell_length_a                   14.1251(4)
_cell_length_b                   23.5850(6)
_cell_length_c                   23.8891(5)
_cell_measurement_reflns_used    29961
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      72.7430
_cell_measurement_theta_min      4.1720
_cell_volume                     7505.2(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      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1150
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.988
_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_R_equivalents  0.0523
_diffrn_reflns_av_unetI/netI     0.0557
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            88483
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.905
_diffrn_reflns_theta_min         3.864
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.545
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85447
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.401
_exptl_crystal_description       block
_exptl_crystal_F_000             3257
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene, n-hexane'
_exptl_crystal_size_max          0.060
_exptl_crystal_size_mid          0.060
_exptl_crystal_size_min          0.040
_refine_diff_density_max         1.113
_refine_diff_density_min         -0.783
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1900
_refine_ls_number_reflns         29616
_refine_ls_number_restraints     192
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0625
_refine_ls_R_factor_gt           0.0432
_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^)+(0.0527P)^2^+5.2887P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1021
_refine_ls_wR_factor_ref         0.1130
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22967
_reflns_number_total             29616
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cy01032a2.cif
_cod_data_source_block           s22uh21
_cod_depositor_comments
'Adding full bibliography for 1573241--1573249.cif.'
_cod_database_code               1573248
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.772
_shelx_estimated_absorpt_t_max   0.839
_oxdiff_exptl_absorpt_empirical_full_min 0.614
_oxdiff_exptl_absorpt_empirical_full_max 1.295
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_shelx_res_checksum              40921