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_1576789
_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         'C44 H57 La S, C6 H14'
_chemical_formula_sum            'C50 H71 La S'
_chemical_formula_weight         843.03
_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   geom
_atom_sites_solution_primary     direct
_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                 113.2280(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.9455(6)
_cell_length_b                   15.7077(5)
_cell_length_c                   18.2737(6)
_cell_measurement_reflns_used    9837
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      29.15
_cell_measurement_theta_min      2.26
_cell_volume                     4469.7(3)
_computing_cell_refinement       'Bruker SAINT 8.34a, 2013'
_computing_data_collection       'Bruker APEX2 2014.11-0, 2014'
_computing_data_reduction        'Bruker SAINT 8.34a, 2013'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'Bruker SHELXTL 2014/4 (XT)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.0649
_diffrn_reflns_av_unetI/netI     0.0479
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            87421
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.507
_diffrn_reflns_theta_min         1.775
_diffrn_source_current           1.6
_diffrn_source_power             0.08
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.034
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.7143
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1138 before and 0.0680 after correction.
The Ratio of minimum to maximum transmission is 0.9574.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.253
_exptl_crystal_density_meas      ?
_exptl_crystal_description       Irregular
_exptl_crystal_F_000             1776
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane'
_exptl_crystal_size_max          0.125
_exptl_crystal_size_mid          0.065
_exptl_crystal_size_min          0.054
_refine_diff_density_max         0.979
_refine_diff_density_min         -0.679
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.009
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     720
_refine_ls_number_reflns         13635
_refine_ls_number_restraints     541
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0739
_refine_ls_R_factor_gt           0.0427
_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^)+(0.0395P)^2^+4.4131P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0905
_refine_ls_wR_factor_ref         0.1030
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9832
_reflns_number_total             13635
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc00248j2.cif
_cod_data_source_block           mrl59
_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_database_code               1576789
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.946
_shelx_estimated_absorpt_t_min   0.882
_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
 C32A-C31A \\sim C32-C31 \\sim C33A-C31A \\sim C33-C31
 with sigma of 0.02
 S1A-C1 \\sim S1-C1
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C40A \\sim C39 \\sim C39A \\sim C38 \\sim C38A \\sim C37A \\sim C37 \\sim C44A
\\sim C44 \\sim C43A \\sim C43 \\sim C42 \\sim C42A \\sim C41 \\sim C41A \\sim
C40: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C26A \\sim C26 \\sim C25A \\sim C25 \\sim C24A \\sim C24 \\sim C22A \\sim C22
\\sim C27 \\sim C27A \\sim C32A \\sim C31A \\sim C32 \\sim C33A \\sim C31 \\sim
C33 \\sim C23: within 2A with sigma of 0.003 and sigma for terminal atoms of
0.006 within 2A
C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C45A \\sim C46A \\sim C47A \\sim C48A \\sim C49A \\sim C50A: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
4. Others
 Fixed Sof: La1(0.5) La1A(0.5) S1(0.5) S1A(0.5) C22A(0.5) C24A(0.5) H24A(0.5)
 C25A(0.5) C26(0.5) H26(0.5) C27(0.5) C22(0.5) C24(0.5) H24(0.5) C25(0.5)
 C26A(0.5) H26A(0.5) C27A(0.5) C31(0.5) H31(0.5) C31A(0.5) H31A(0.5) C32(0.5)
 H32A(0.5) H32B(0.5) H32C(0.5) C32A(0.5) H32D(0.5) H32E(0.5) H32F(0.5) C33(0.5)
 H33A(0.5) H33B(0.5) H33C(0.5) C33A(0.5) H33D(0.5) H33E(0.5) H33F(0.5) C34(0.5)
 H34(0.5) C34A(0.5) H34A(0.5) C35(0.5) H35A(0.5) H35B(0.5) H35C(0.5) C35A(0.5)
 H35D(0.5) H35E(0.5) H35F(0.5) C36(0.5) H36A(0.5) H36B(0.5) H36C(0.5) C36A(0.5)
 H36D(0.5) H36E(0.5) H36F(0.5) C37(0.5) H37(0.5) C37A(0.5) H37A(0.5) C38(0.5)
 H38(0.5) C38A(0.5) H38A(0.5) C39(0.5) H39(0.5) C39A(0.5) H39A(0.5) C40(0.5)
 H40(0.5) C40A(0.5) H40A(0.5) C41(0.5) H41(0.5) C41A(0.5) H41A(0.5) C42(0.5)
 H42(0.5) C42A(0.5) H42A(0.5) C43(0.5) H43(0.5) C43A(0.5) H43A(0.5) C44(0.5)
 H44(0.5) C44A(0.5) H44A(0.5) C45(0.5) H45A(0.5) H45B(0.5) H45C(0.5) C45A(0.5)
 H45D(0.5) H45E(0.5) H45F(0.5) C46(0.5) H46A(0.5) H46B(0.5) C46A(0.5) H46C(0.5)
 H46D(0.5) C47(0.5) H47A(0.5) H47B(0.5) C47A(0.5) H47C(0.5) H47D(0.5) C48(0.5)
 H48A(0.5) H48B(0.5) C48A(0.5) H48C(0.5) H48D(0.5) C49(0.5) H49A(0.5) H49B(0.5)
 C49A(0.5) H49C(0.5) H49D(0.5) C50(0.5) H50A(0.5) H50B(0.5) H50C(0.5) C50A(0.5)
 H50D(0.5) H50E(0.5) H50F(0.5)
5.a Ternary CH refined with riding coordinates:
 C13(H13), C16(H16), C19(H19), C28(H28), C31(H31), C31A(H31A), C34(H34),
 C34A(H34A)
5.b Secondary CH2 refined with riding coordinates:
 C46(H46A,H46B), C46A(H46C,H46D), C47(H47A,H47B), C47A(H47C,H47D), C48(H48A,
 H48B), C48A(H48C,H48D), C49(H49A,H49B), C49A(H49C,H49D)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C9(H9), C11(H11), C24A(H24A), C26(H26), C24(H24),
 C26A(H26A), C37(H37), C37A(H37A), C38(H38), C38A(H38A), C39(H39), C39A(H39A),
 C40(H40), C40A(H40A), C41(H41), C41A(H41A), C42(H42), C42A(H42A), C43(H43),
 C43A(H43A), C44(H44), C44A(H44A)
5.d Fitted hexagon refined as free rotating group:
 C26(C27,C22,C23,C24,C25)
5.e Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C32(H32A,H32B,H32C), C32A(H32D,H32E,H32F), C33(H33A,H33B,H33C),
 C33A(H33D,H33E,H33F), C35(H35A,H35B,H35C), C35A(H35D,H35E,H35F), C36(H36A,H36B,
 H36C), C36A(H36D,H36E,H36F), C45(H45A,H45B,H45C), C45A(H45D,H45E,H45F),
 C50(H50A,H50B,H50C), C50A(H50D,H50E,H50F)
;
_shelx_res_checksum              35847
_olex2_submission_special_instructions 'No special instructions were received'