Identification of Au-hydrides as key intermediates in the reduction of Au(iii) prodrugs to active Au(i) species under protic conditions.
Ochs, Jasmine; Metzler-Nolte, Nils; Chemical science 17 (2026) 4183–4190; doi:10.1039/d5sc06212h

data_1576655
_publ_section_title
;
 Identification of Au-hydrides as key intermediates in the reduction of
 Au(iii) prodrugs to active Au(i) species under protic conditions.
;
_journal_issue                   8
_journal_name_full               'Chemical science'
_journal_page_first              4183
_journal_page_last               4190
_journal_paper_doi               10.1039/d5sc06212h
_journal_volume                  17
_journal_year                    2026
_chemical_absolute_configuration unk
_chemical_formula_moiety
'2(C15 H17 Au Cl N2 O2 S), C H4 O, 1.774(Cl), C H4 Cl0.226 O'
_chemical_formula_sum            'C32 H42 Au2 Cl4 N4 O6 S2'
_chemical_formula_weight         1178.589
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_Int_Tables_number      4
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-02-11
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2025-02-17 deposited with the CCDC.	2025-12-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 115.370(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   17.2761(3)
_cell_length_b                   6.7454(1)
_cell_length_c                   18.9344(3)
_cell_measurement_reflns_used    10432
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      76.1140
_cell_measurement_theta_min      2.8920
_cell_volume                     1993.71(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(3)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9970
_diffrn_measured_fraction_theta_max 0.9453
_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    107.00 154.00   0.50    1.64    --  105.91  95.00  18.00   94
  2  \w     93.00 177.00   0.50    1.64    --  105.91  30.00   0.00  168
  3  \w     93.00 178.00   0.50    1.64    --  105.91  30.00 -30.00  170
  4  \w     -5.00  47.00   0.50    0.42    --   47.03 -95.00 -91.00  104
  5  \w     49.00  75.00   0.50    1.64    --  105.91 -95.00 -91.00   52
  6  \w     73.00 106.00   0.50    1.64    --  105.91 -94.00 -90.00   66
  7  \w     53.00 106.00   0.50    1.64    --  105.91 -94.00 -60.00  106
  8  \w     43.00  69.00   0.50    1.64    --  105.91 -61.00 -30.00   52
  9  \w     34.00  74.00   0.50    1.64    --  105.91 -61.00-120.00   80
 10  \w     41.00  71.00   0.50    1.64    --  105.91 -61.00 -60.00   60
 11  \w     36.00  65.00   0.50    1.64    --  105.91 -61.00   0.00   58
 12  \w     33.00  58.00   0.50    1.64    --  105.91 -61.00 150.00   50
 13  \w    -48.00 -23.00   0.50    1.64    --  -91.75  45.00-180.00   50
 14  \w    -64.00 -24.00   0.50    1.64    --  -91.75  61.00-150.00   80
 15  \w    -48.00 -21.00   0.50    1.64    --  -91.75  45.00-150.00   54
 16  \w    -46.00 -21.00   0.50    1.64    --  -91.75  45.00-120.00   50
 17  \w    -47.00 -21.00   0.50    1.64    --  -91.75  45.00 -60.00   52
 18  \w    -40.00  24.00   0.50    0.42    --  -47.03  38.00 -90.00  128
 19  \w     -3.00  28.00   0.50    0.42    --  -47.03  19.00 120.00   62
 20  \w    -78.00 -48.00   0.50    1.64    --  -91.75  95.00  18.00   60
 21  \w    -77.00  18.00   0.50    0.42    --  -47.03  95.00  18.00  190
 22  \w   -148.00-115.00   0.50    1.64    --  -91.75 -95.00 -91.00   66
 23  \w   -113.00 -88.00   0.50    0.42    --  -47.03-125.00 -30.00   50
 24  \w   -119.00 -77.00   0.50    0.42    --  -47.03-125.00  60.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0000024000
_diffrn_orient_matrix_UB_12      0.1714071000
_diffrn_orient_matrix_UB_13      -0.0537733000
_diffrn_orient_matrix_UB_21      0.0537223000
_diffrn_orient_matrix_UB_22      -0.1266815000
_diffrn_orient_matrix_UB_23      -0.0302537000
_diffrn_orient_matrix_UB_31      -0.0828076000
_diffrn_orient_matrix_UB_32      -0.0819184000
_diffrn_orient_matrix_UB_33      -0.0655649000
_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  0.0392
_diffrn_reflns_av_unetI/netI     0.0419
_diffrn_reflns_Laue_measured_fraction_full 0.9970
_diffrn_reflns_Laue_measured_fraction_max 0.9453
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            13529
_diffrn_reflns_point_group_measured_fraction_full 0.7831
_diffrn_reflns_point_group_measured_fraction_max 0.7252
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         76.69
_diffrn_reflns_theta_min         2.58
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    17.464
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55608
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.963
_exptl_crystal_description       needle
_exptl_crystal_F_000             1128.102
_exptl_crystal_recrystallization_method
'grwon by slow evaporation of diethylether inside a DCM/methanol mixture'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.01
_refine_diff_density_max         2.2328
_refine_diff_density_min         -1.0602
_refine_diff_density_rms         0.1602
_refine_ls_abs_structure_details
'Hooft, R.W.W., Straver, L.H., Spek, A.L. (2010). J. Appl. Cryst., 43, 665-668.'
_refine_ls_abs_structure_Flack   0.018(10)
_refine_ls_d_res_high            0.7922
_refine_ls_d_res_low             17.1084
_refine_ls_goodness_of_fit_ref   1.0391
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    69
_refine_ls_number_parameters     472
_refine_ls_number_reflns         6100
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.0391
_refine_ls_R_factor_all          0.0365
_refine_ls_R_factor_gt           0.0352
_refine_ls_shift/su_max          0.0010
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0730P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0962
_refine_ls_wR_factor_ref         0.0969
_reflns_Friedel_coverage         0.463
_reflns_limit_h_max              21
_reflns_limit_h_min              -21
_reflns_limit_k_max              6
_reflns_limit_k_min              -8
_reflns_limit_l_max              23
_reflns_limit_l_min              -23
_reflns_number_gt                5860
_reflns_number_total             6100
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5sc06212h2.cif
_cod_data_source_block           JO_MA_07_auto_a
_cod_original_sg_symbol_Hall     ' P 2yb'
_cod_database_code               1576655
_chemical_oxdiff_formula         CHNSAu
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Others
 Sof(Cl3B)=1-FVAR(1)
 Sof(Cl3A)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C13(H13), C13A(H13A)
3.b Secondary CH2 refined with riding coordinates:
 C12(H12a,H12b), C12A(H12c,H12d)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C2A(H2Aa), C3(H3), C3A(H3A), C5(H5), C5A(H5A), C8(H8), C8A(H8A),
 C9(H9), C9A(H9A), C10(H10), C10A(H10A), C11(H11), C11A(H11A), C4(H4), C4A(H4A)
3.d Idealised Me refined as rotating group:
 N2(H2a,H2b,H2c), C2S(H2Sa,H2Sb,H2Sc), C15(H15a,H15b,H15c), C15A(H15d,H15e,
 H15f), N1A(H1Aa,H1Ab,H1Ac), C1S(H1Sa,H1Sb,H1Sc)
3.e Idealised tetrahedral OH refined as rotating group:
 O1S(H3B)
;
_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 2.212
_oxdiff_exptl_absorpt_empirical_full_min 0.468