Tuning the reactivity of an osmium-peroxo unit by modulating metallacycle aromaticity.
Deng, Zhihong; Zhang, Hong; Luo, Ming; Xia, Haiping; Chemical communications (Cambridge, England) 62 (2026) 5914–5918; doi:10.1039/d5cc07078c

data_7135412
_publ_section_title
;
 Tuning the reactivity of an osmium-peroxo unit by modulating metallacycle
 aromaticity.
;
_journal_issue                   21
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              5914
_journal_page_last               5918
_journal_paper_doi               10.1039/d5cc07078c
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety         'C63 H52 O4 Os P3, C24 H20 B, 1.5(C H2 Cl2)'
_chemical_formula_sum            'C88.5 H75 B Cl3 O4 Os P3'
_chemical_formula_weight         1602.75
_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
_audit_creation_date             2024-09-14
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-12-12 deposited with the CCDC.	2026-02-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.580(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.0065(3)
_cell_length_b                   24.5208(5)
_cell_length_c                   23.9619(5)
_cell_measurement_reflns_used    9899
_cell_measurement_temperature    181(2)
_cell_measurement_theta_max      29.0900
_cell_measurement_theta_min      2.5020
_cell_volume                     7591.8(3)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      181(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'SuperNova, Dual, Mo at zero, Atlas'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0404
_diffrn_reflns_av_unetI/netI     0.0486
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            46781
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.499
_diffrn_reflns_theta_min         2.190
_exptl_absorpt_coefficient_mu    1.900
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65571
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic brownish orange'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.402
_exptl_crystal_description       block
_exptl_crystal_F_000             3260
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.515
_refine_diff_density_min         -1.340
_refine_diff_density_rms         0.101
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     948
_refine_ls_number_reflns         17402
_refine_ls_number_restraints     105
_refine_ls_restrained_S_all      1.107
_refine_ls_R_factor_all          0.0625
_refine_ls_R_factor_gt           0.0479
_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^)+(0.0281P)^2^+20.9634P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0977
_refine_ls_wR_factor_ref         0.1022
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14502
_reflns_number_total             17402
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc07078c2.cif
_cod_data_source_block           dzh151126-1-original
_cod_depositor_comments
'Adding full bibliography for 7135412--7135413.cif.'
_cod_original_cell_volume        7591.9(3)
_cod_original_formula_sum        'C88.50 H75 B Cl3 O4 Os P3'
_cod_database_code               7135412
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.702
_shelx_estimated_absorpt_t_min   0.599
_olex2_refinement_description
;
1. Restrained distances
 C1A-Cl1A
 1.77 with sigma of 0.02
 C1A-Cl1
 1.77 with sigma of 0.02
 C0-Cl2
 1.77 with sigma of 0.02
2. Uiso/Uaniso restraints and constraints
C89 \\sim Cl4 \\sim Cl0A \\sim Cl3: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Cl2 \\sim Cl1 \\sim C0 \\sim C1A \\sim Cl1A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C70 \\sim C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
3. Others
 Fixed Sof: Cl4(0.65) H89A(0.65) H89B(0.65) H89C(0.35) H89D(0.35) Cl0A(0.35)
 Cl1(0.5) Cl2(0.25) C0(0.25) H0A(0.25) H0B(0.25) Cl1A(0.25) C1A(0.25)
 H1AA(0.25) H1AB(0.25)
4.a Rotating group:
 O1(H1)
4.b Secondary CH2 refined with riding coordinates:
 C89(H89A,H89B), C89(H89C,H89D), C0(H0A,H0B), C1A(H1AA,H1AB)
4.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C5(H5), C51(H51), C59(H59), C15(H15), C63(H63), C49(H49),
 C17(H17), C23(H23), C21(H21), C48(H48), C11(H11), C45(H45), C57(H57), C47(H47),
  C54(H54), C27(H27), C53(H53), C55(H55), C44(H44), C18(H18), C42(H42),
 C24(H24), C87(H87), C33(H33), C14(H14), C50(H50), C41(H41), C25(H25), C19(H19),
  C12(H12), C35(H35), C20(H20), C56(H56), C13(H13), C62(H62), C60(H60),
 C29(H29), C31(H31), C39(H39), C43(H43), C77(H77), C26(H26), C32(H32), C83(H83),
  C61(H61), C79(H79), C75(H75), C81(H81), C30(H30), C85(H85), C38(H38),
 C71(H71), C84(H84), C37(H37), C36(H36), C80(H80), C86(H86), C73(H73), C65(H65),
  C72(H72), C69(H69), C78(H78), C67(H67), C66(H66), C74(H74), C68(H68)
4.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C)
;
_shelx_res_checksum              88671
_shelx_hkl_checksum              64063
_olex2_submission_special_instructions 'No special instructions were received'