Unexpected dispersion-stabilized tris(terphenylthiolate) complexes, Ln(SAriPr6)3, arising from two-electron reduction by Ln(SAriPr6)2 [AriPr6 = C6H3-2,6-(C6H2-2,6,4-iPr3)2]
Luevano, Makayla R.; Stennett, Cary R.; Ma, Eric; Ziller, Joseph W.; Furche, Filipp; Evans, William J.; Chemical Science  (2026) –; doi:10.1039/D6SC00248J

data_1576787
_publ_section_title
;
 Unexpected dispersion-stabilized tris(terphenylthiolate) complexes,
 Ln(SAr <sup><i>i</i>Pr6</sup>)<sub>3</sub>, arising from two-electron
 reduction by Ln(SAr <sup><i>i</i>Pr6</sup>)<sub>2</sub> [Ar
 <sup><i>i</i>Pr6</sup> =
 C<sub>6</sub>H<sub>3</sub>-2,6-(C<sub>6</sub>H<sub>2</sub>-2,6,4-
 <sup><i>i</i></sup> Pr<sub>3</sub>)<sub>2</sub>].
;
_journal_issue                   16
_journal_name_full               'Chemical science'
_journal_page_first              8160
_journal_page_last               8167
_journal_paper_doi               10.1039/d6sc00248j
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C108 H147 La S3'
_chemical_formula_sum            'C108 H147 La S3'
_chemical_formula_weight         1680.34
_chemical_melting_point          ?
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-12-19
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-12-19 deposited with the CCDC.	2026-02-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.2320(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.8533(10)
_cell_length_b                   44.125(3)
_cell_length_c                   16.4431(11)
_cell_measurement_reflns_used    9894
_cell_measurement_temperature    100.11
_cell_measurement_theta_max      29.18
_cell_measurement_theta_min      2.20
_cell_volume                     10605.4(12)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Bruker APEX2 2014.11-0, 2014'
_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    'Bruker SHELXTL 2014/4 (XT)'
_diffrn_ambient_temperature      100.11
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0754
_diffrn_reflns_av_unetI/netI     0.0714
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       63
_diffrn_reflns_limit_k_min       -63
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            142360
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.540
_diffrn_reflns_theta_min         1.671
_diffrn_source                   'Bruker IuS'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.503
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6916
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0377 before and 0.0352 after correction.
The Ratio of minimum to maximum transmission is 0.9270.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.052
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             3600
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: diethyl ether'
_exptl_crystal_size_max          0.178
_exptl_crystal_size_mid          0.104
_exptl_crystal_size_min          0.084
_refine_diff_density_max         0.851
_refine_diff_density_min         -0.952
_refine_diff_density_rms         0.086
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1431
_refine_ls_number_reflns         32455
_refine_ls_number_restraints     54
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0820
_refine_ls_R_factor_gt           0.0521
_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^)+(0.0509P)^2^+5.1548P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1046
_refine_ls_wR_factor_ref         0.1136
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23110
_reflns_number_total             32455
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc00248j2.cif
_cod_data_source_block           mrl47
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value 'not measured' was changed
to '?' -- the value is undefined or not given.

data item '_exptl_crystal_density_meas' value 'not measured' was
changed to '?' -- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1576785--1576790.cif.
;
_cod_original_cell_volume        10605.5(13)
_cod_database_code               1576787
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.916
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C57-C55
 1.55 with sigma of 0.02
 C57A-C55
 1.55 with sigma of 0.02
 C65A-C64 = C65-C64
 1.55 with sigma of 0.02
 C57-C55 \\sim C57A-C55
 with sigma of 0.02
 C65A-C64 \\sim C65-C64
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C69 \\sim C67 \\sim C68A \\sim C68: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
C66 \\sim C64 \\sim C65A \\sim C65: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
4. Others
 Fixed Sof: H64(0.5) H64A(0.5) C65(0.5) H65A(0.5) H65B(0.5) H65C(0.5) H55(0.5)
 H55A(0.5) C57(0.5) H57A(0.5) H57B(0.5) H57C(0.5) H67(0.6) H67A(0.4) C68(0.6)
 H68A(0.6) H68B(0.6) H68C(0.6) C68A(0.4) H68D(0.4) H68E(0.4) H68F(0.4)
 C65A(0.5) H65D(0.5) H65E(0.5) H65F(0.5) C57A(0.5) H57D(0.5) H57E(0.5) H57F(0.5)
5.a Ternary CH refined with riding coordinates:
 C88(H88), C103(H103), C64(H64), C64(H64A), C55(H55), C55(H55A), C67(H67),
 C67(H67A)
5.b Idealised Me refined as rotating group:
 C87(H87A,H87B,H87C), C29(H29A,H29B,H29C), C54(H54A,H54B,H54C), C33(H33A,H33B,
 H33C), C15(H15A,H15B,H15C), C72(H72A,H72B,H72C), C108(H10A,H10B,H10C),
 C102(H10J,H10K,H10L), C104(H10M,H10N,H10O), C65(H65A,H65B,H65C), C66(H66A,H66B,
 H66C), C105(H10P,H10Q,H10R), C57(H57A,H57B,H57C), C56(H56A,H56B,H56C),
 C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C68A(H68D,H68E,H68F), C65A(H65D,H65E,
 H65F), C57A(H57D,H57E,H57F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              60631
_shelx_fab_checksum              60580
_olex2_submission_special_instructions 'No special instructions were received'