Crystallographic Evidence of a Trinuclear (salen)Manganese(IV/III/IV)-μ-Oxo Formed during Catalytic C(sp3)–H Oxidation Reactions
Paul, Bhaswati; Dabare, Kusalvin; Bocarsly, Joshua D.; Mills, L. Reginald; Dalton Transactions  (2026) –; doi:10.1039/D5DT02844B

data_7720014
_publ_section_title
;
 Crystallographic Evidence of a Trinuclear
 (salen)Manganese(IV/III/IV)-\m-Oxo Formed during Catalytic C(sp3)--H
 Oxidation Reactions
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D5DT02844B
_journal_year                    2026
_chemical_formula_moiety
'C108 H155 Mn3 N6 O8, C11 O2, F6 P, 1.5(C2 H3 N), H2 O'
_chemical_formula_sum            'C122 H161.5 F6 Mn3 N7.5 O11 P'
_chemical_formula_weight         2218.87
_chemical_name_systematic        BP_Mn1_PhIO
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-31
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-08-30 deposited with the CCDC.	2025-12-10 downloaded from the CCDC.
;
_cell_angle_alpha                102.8620(10)
_cell_angle_beta                 98.7220(10)
_cell_angle_gamma                97.8240(10)
_cell_formula_units_Z            2
_cell_length_a                   13.8836(2)
_cell_length_b                   19.2316(3)
_cell_length_c                   23.6564(4)
_cell_measurement_reflns_used    9427
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      68.28
_cell_measurement_theta_min      3.70
_cell_volume                     5991.32(17)
_computing_cell_refinement       'SAINT V8.41 (?, 2016)'
_computing_data_reduction        'SAINT V8.41 (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0421
_diffrn_reflns_av_unetI/netI     0.0308
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            96266
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.377
_diffrn_reflns_theta_min         3.272
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.1
_diffrn_source_power             0.05500000000000001
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.217
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6209
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0901 before and 0.0482 after correction.
The Ratio of minimum to maximum transmission is 0.8245.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear brownish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.230
_exptl_crystal_description       plate
_exptl_crystal_F_000             2356
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.314
_refine_diff_density_min         -0.984
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1486
_refine_ls_number_reflns         21872
_refine_ls_number_restraints     691
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0725
_refine_ls_R_factor_gt           0.0649
_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^)+(0.1157P)^2^+10.4937P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1867
_refine_ls_wR_factor_ref         0.1942
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19219
_reflns_number_total             21872
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02844b2.cif
_cod_data_source_block           cu_bp_mn1_phio_0m_a
_cod_original_sg_symbol_H-M      P-1
_cod_original_formula_sum        'C122 H161.50 F6 Mn3 N7.50 O11 P'
_cod_database_code               7720014
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.856
_shelx_estimated_absorpt_t_min   0.739
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C78B_1-C73A \\sim C78A-C73B_1 \\sim C74_1-C73A \\sim C74_1-C73B_1 \\sim
C75A-C74_1 \\sim C75B_1-
 C74_1 \\sim C76B_1-C75A \\sim C76A-C75B_1 \\sim C77_1-C76A \\sim C77_1-C76B_1
\\sim C78A-C77_1 ~
 C78B_1-C77_1
 with sigma of 0.02
 N5_1-C73A \\sim N5_1-C73B_1 \\sim N6_1-C78A \\sim N6_1-C78B_1
 with sigma of 0.02
 C38A-C37A \\sim C38B_1-C37B_1 \\sim C42_1-C37A \\sim C42_1-C37B_1 \\sim
C42_1-C41A \\sim C42_1-
 C41B_1 \\sim C41B_1-C40B_1 \\sim C41A-C40A \\sim C40A-C39_1 \\sim C40B_1-C39_1
\\sim C39_1-C38A ~
 C39_1-C38B_1
 with sigma of 0.02
 N3_1-C38A \\sim N3_1-C38B_1 \\sim N4_1-C37A \\sim N4_1-C37B_1
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C6_2 \\sim C3_2 \\sim C4_2 \\sim C2_2 \\sim C10_2 \\sim C5_2 \\sim C1_2 \\sim
C11_2 \\sim C8_2 \\sim C7_2 \\sim O2_2 \\sim O1_2: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
C73A \\sim C78A \\sim C73B_1 \\sim C78B_1 \\sim C75A \\sim C75B_1 \\sim C76A
\\sim C76B_1 \\sim C74_1 \\sim C77_1: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C37A \\sim C38A \\sim C37B_1 \\sim C38B_1 \\sim C41A \\sim C40A \\sim C41B_1
\\sim C40B_1 \\sim C39_1 \\sim C42_1: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
Uanis(C1_6) \\sim Ueq, Uanis(C2_6) \\sim Ueq, Uanis(N1_6) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C87_1) \\sim Ueq, Uanis(C89_1) \\sim Ueq, Uanis(C88_1) \\sim Ueq,
Uanis(C66_1) \\sim Ueq, Uanis(C67_1) \\sim Ueq, Uanis(C68_1) \\sim Ueq: with
sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C88_1) \\sim Ueq, Uanis(C87_1) \\sim Ueq, Uanis(C89_1) \\sim Ueq,
Uanis(C66_1) \\sim Ueq, Uanis(C67_1) \\sim Ueq, Uanis(C68_1) \\sim Ueq: with
sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C2_2, C3_2, C4_2, C10_2, C5_2, C1_2, C11_2, C6_2, C8_2, C7_2, O2_2, O1_2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C73A, C78A, C73B_1, C78B_1, C77_1, C74_1, C75A, C76B_1, C76A, C75B_1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C37A, C37B_1, C38A, C38B_1, C42_1, C41A, C41B_1, C40A, C40B_1, C39_1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C78A)=Sof(H78A)=Sof(C76A)=Sof(H76A)=Sof(H76B)=Sof(C37A)=Sof(H37A)=
 Sof(C41A)=Sof(H41A)=Sof(H41B)=Sof(C38B)=Sof(H38B)=Sof(H42C)=Sof(H42D)=
 Sof(H39C)=Sof(H39D)=Sof(C73B)=Sof(H73B)=Sof(C40B)=Sof(H40A)=Sof(H40B)=
 Sof(H74C)=Sof(H74D)=Sof(H77C)=Sof(H77D)=Sof(C75B)=Sof(H75A)=Sof(H75B)=1-FVAR(1)
 Sof(C73A)=Sof(H73A)=Sof(C75A)=Sof(H75A)=Sof(H75B)=Sof(C38A)=Sof(H38A)=
 Sof(C40A)=Sof(H40A)=Sof(H40B)=Sof(C37B)=Sof(H37B)=Sof(H42A)=Sof(H42B)=
 Sof(H39A)=Sof(H39B)=Sof(C78B)=Sof(H78B)=Sof(C41B)=Sof(H41A)=Sof(H41B)=
 Sof(H74A)=Sof(H74B)=Sof(H77A)=Sof(H77B)=Sof(C76B)=Sof(H76A)=Sof(H76B)=FVAR(1)
 Fixed Sof: C2(0.5) N1(0.5) C1(0.5) H1A(0.5) H1B(0.5) H1C(0.5)
6.a Free rotating group:
 O1(H1A,H1B)
6.b Ternary CH refined with riding coordinates:
 C73A(H73A), C78A(H78A), C37A(H37A), C38A(H38A), C6(H6), C1(H1), C37B(H37B),
 C38B(H38B), C73B(H73B), C78B(H78B)
6.c Secondary CH2 refined with riding coordinates:
 C75A(H75A,H75B), C76A(H76A,H76B), C41A(H41A,H41B), C40A(H40A,H40B), C5(H5A,
 H5B), C2(H2A,H2B), C4(H4A,H4B), C42(H42A,H42B), C42(H42C,H42D), C39(H39C,H39D),
  C39(H39A,H39B), C41B(H41A,H41B), C40B(H40A,H40B), C74(H74A,H74B), C74(H74C,
 H74D), C77(H77C,H77D), C77(H77A,H77B), C75B(H75A,H75B), C76B(H76A,H76B)
6.d Aromatic/amide H refined with riding coordinates:
 C7(H7), C22(H22), C58(H58), C43(H43), C13(H13), C11(H11), C24(H24), C26(H26),
 C49(H49), C47(H47), C64(H64), C62(H62), C94(H94), C79(H79), C85(H85), C83(H83),
  C96(H96), C98(H98)
6.e Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C20(H20A,H20B,H20C), C34(H34A,H34B,
 H34C), C36(H36A,H36B,H36C), C35(H35A,H35B,H35C), C55(H55A,H55B,H55C), C56(H56A,
 H56B,H56C), C57(H57A,H57B,H57C), C72(H72A,H72B,H72C), C70(H70A,H70B,H70C),
 C71(H71A,H71B,H71C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C15(H15A,H15B,
 H15C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C30(H30A,H30B,H30C), C53(H53A,
 H53B,H53C), C52(H52A,H52B,H52C), C51(H51A,H51B,H51C), C68(H68A,H68B,H68C),
 C67(H67A,H67B,H67C), C66(H66A,H66B,H66C), C91(H91A,H91B,H91C), C92(H92A,H92B,
 H92C), C93(H93A,H93B,H93C), C106(H10A,H10B,H10C), C107(H10D,H10E,H10F),
 C108(H10G,H10H,H10I), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C89(H89A,H89B,
 H89C), C103(H10J,H10K,H10L), C104(H10M,H10N,H10O), C102(H10P,H10Q,H10R),
 C2(H2A,H2B,H2C), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              60715
_olex2_submission_special_instructions 'No special instructions were received'