An-imidophosphorane (An = U-Pu) bond covalency and proton-coupled electron transfer thermodynamics driven by orbital energy matching.
Studvick, Chad M.; Dey, Sourav; Engle, Kaitlyn S.; Niklas, Julie E.; Sprosty, Jonah W.; La Pierre, Henry S.; Popov, Ivan A.; Physical chemistry chemical physics : PCCP 28 (2026) 6687–6702; doi:10.1039/d6cp00281a

data_7251588
_publ_section_title
;
 An-imidophosphorane (An = U-Pu) bond covalency and proton-coupled
 electron transfer thermodynamics driven by orbital energy matching.
;
_journal_issue                   11
_journal_name_full               'Physical chemistry chemical physics : PCCP'
_journal_page_first              6687
_journal_page_last               6702
_journal_paper_doi               10.1039/d6cp00281a
_journal_volume                  28
_journal_year                    2026
_chemical_formula_moiety         'C48 H101 N12 P4 U, B C24 F20'
_chemical_formula_sum            'C72 H101 B F20 N12 P4 U'
_chemical_formula_weight         1887.36
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-04-21
_audit_creation_method
;FinalCif V125 by Daniel Kratzert, Freiburg 2025, 
https://dkratzert.de/finalcif.html
;
_audit_update_record
;
2025-04-22 deposited with the CCDC.	2026-02-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.377(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.3244(11)
_cell_length_b                   15.4347(14)
_cell_length_c                   39.283(3)
_cell_measurement_reflns_used    9829
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.113
_cell_measurement_theta_min      2.454
_cell_volume                     8028.9(12)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_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  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00
_diffrn_detector                 CPAD
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'Bruker PHOTON III'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE dual wavelength Mo/Cu'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_measurement_specimen_support 'nylon loop'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0988
_diffrn_reflns_av_unetI/netI     0.0355
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            198824
_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         25.349
_diffrn_reflns_theta_min         2.026
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.35
_diffrn_source_power             0.0675
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    2.197
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6076
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1131 before and 0.0801 after correction.
The Ratio of minimum to maximum transmission is 0.8151.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            pink
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.561
_exptl_crystal_description       block
_exptl_crystal_F_000             3816
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.345
_exptl_crystal_size_mid          0.207
_exptl_crystal_size_min          0.171
_refine_diff_density_max         1.193
_refine_diff_density_min         -0.871
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1099
_refine_ls_number_reflns         14688
_refine_ls_number_restraints     322
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0558
_refine_ls_R_factor_gt           0.0430
_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^)+(0.0383P)^2^+25.3060P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0985
_refine_ls_wR_factor_ref         0.1046
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12237
_reflns_number_total             14688
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cp00281a2.cif
_cod_data_source_block           kse15_b388
_cod_depositor_comments          'Adding full bibliography for 7251588.cif.'
_cod_database_code               7251588
_diffrn_oxdiff_ac3_digest_hkl    41f1dbe4bc8f2a239cb61b92c431a61af16665
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C11G-C10G = C10G-C9G = C9G-N2B = N2B-C12G = C12G-C11G
 1.39 with sigma of 0.01
 C1G-C4G = C1G-C2G = C1G-C3G
 1.52 with sigma of 0.02
 P1B-C1G
 1.84 with sigma of 0.02
 N2B-C12G = N2B-C9G
 1.45 with sigma of 0.02
 C5G-C6G = C6G-C7G = C7G-C8G = C9G-C10G = C10G-C11G = C11G-C12G
 1.48 with sigma of 0.04
 N2B-C12G = N2B-C9G = N1G-C8G = N1G-C5G
 1.46 with sigma of 0.04
 N1A-N1B \\sim N1C-N1F
 with sigma of 0.001
 C2D-C3D \\sim C3D-C4D \\sim C4D-C2D
 with sigma of 0.02
 C1D-C2D \\sim C1D-C3D \\sim C1D-C4D
 with sigma of 0.02
3. Restrained planarity
 N1G, C5G, C6G, C7G, C8G
 with sigma of 0.1
4. Rigid bond restraints
 F6, F7, F8, F9, F10, C8, C9, C10, C11, C12
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C1D, C1D, C1D, C2D, C3D, C4D
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C9C, C10C, C10C, C11C, C11C, C12C, C5D, C6D, C6D, C7D, C7D, C8D, C9D, C10D,
 C10D, C11D, C11D, C12D
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 N3C, N3C, C9C, C12C, N2D, N2D, N3D, N3D, C5D, C8D, C9D, C12D
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N3C, N3C, C10C, C11C, N2D, N2D, N3D, N3D, C6D, C7D, C10D, C11D
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C1B \\sim C2B \\sim C3B \\sim C4B: within 2A with sigma of 0.002 and sigma for
terminal atoms of 0.004 within 2A
C2D \\sim C3D \\sim C4D: within 2A with sigma of 0.002 and sigma for terminal
atoms of 0.004 within 2A
C9C \\sim C10C \\sim C11C \\sim C12C \\sim C5D \\sim C6D \\sim C7D \\sim C8D
\\sim C9D \\sim C10D \\sim C11D \\sim C12D: within 2A with sigma of 0.002 and
sigma for terminal atoms of 0.004 within 2A
Uanis(C4B) \\sim Ueq, Uanis(C1B) \\sim Ueq, Uanis(C3B) \\sim Ueq, Uanis(C2B)
\\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(F7) \\sim Ueq, Uanis(F8) \\sim Ueq, Uanis(F9) \\sim Ueq: with sigma of
0.002 and sigma for terminal atoms of 0.004
Uanis(C3D) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C8B) = Uanis(C7G)
Uanis(C12B) = Uanis(C12G)
Uanis(C10B) = Uanis(C10G)
Uanis(C11B) = Uanis(C11G)
Uanis(C5B) = Uanis(C5G)
Uanis(N1B) = Uanis(N1G)
Uanis(C8B) = Uanis(C8G)
6. Rigid body (RIGU) restrains
 C2B, C3B, C4B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C9C, C10C, C11C, C12C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F6, F7, F8, F9, F10, C8, C9, C10, C11, C12
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C2D, C2D, C3D, C3D, C4D, C4D
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C1D, C1D, C1D, C2D, C3D, C4D
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.04
 C9C, C10C, C10C, C11C, C11C, C12C, C5D, C6D, C6D, C7D, C7D, C8D, C9D, C10D,
 C10D, C11D, C11D, C12D
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Fixed Sof: N1F(0.4) C1B(0.85) C2B(0.85) H2BA(0.85) H2BB(0.85) H2BC(0.85)
 C3B(0.85) H3BA(0.85) H3BB(0.85) H3BC(0.85) C4B(0.85) H4BA(0.85) H4BB(0.85)
 H4BC(0.85) C5B(0.85) H5BA(0.85) H5BB(0.85) C6B(0.85) H6BA(0.85) H6BB(0.85)
 C7B(0.85) H7BA(0.85) H7BB(0.85) C8B(0.85) H8BA(0.85) H8BB(0.85) C9B(0.85)
 H9BA(0.85) H9BB(0.85) C10B(0.85) H10C(0.85) H10D(0.85) C11B(0.85) H11C(0.85)
 H11D(0.85) C12B(0.85) H12C(0.85) H12D(0.85) N3BA(0.85) N1C(0.6) N1D(0.6)
 H1D(0.6) N1E(0.4) H1E(0.4) N1G(0.15) C1G(0.15) C2G(0.15) H2GA(0.15) H2GB(0.15)
 H2GC(0.15) C3G(0.15) H3GA(0.15) H3GB(0.15) H3GC(0.15) C4G(0.15) H4GA(0.15)
 H4GB(0.15) H4GC(0.15) C5G(0.15) H5GA(0.15) H5GB(0.15) C6G(0.15) H6GA(0.15)
 H6GB(0.15) C7G(0.15) H7GA(0.15) H7GB(0.15) C8G(0.15) H8GA(0.15) H8GB(0.15)
 C9G(0.15) H9GA(0.15) H9GB(0.15) C10G(0.15) H10I(0.15) H10J(0.15) C11G(0.15)
 H11I(0.15) H11J(0.15) C12G(0.15) H12I(0.15) H12J(0.15)
8.a Secondary CH2 refined with riding coordinates:
 C5A(H5AA,H5AB), C6A(H6AA,H6AB), C7A(H7AA,H7AB), C8A(H8AA,H8AB), C9A(H9AA,
 H9AB), C10A(H10A,H10B), C11A(H11A,H11B), C12A(H12A,H12B), C5B(H5BA,H5BB),
 C6B(H6BA,H6BB), C7B(H7BA,H7BB), C8B(H8BA,H8BB), C9B(H9BA,H9BB), C10B(H10C,
 H10D), C11B(H11C,H11D), C12B(H12C,H12D), C5C(H5CA,H5CB), C6C(H6CA,H6CB),
 C7C(H7CA,H7CB), C8C(H8CA,H8CB), C9C(H9CA,H9CB), C10C(H10E,H10F), C11C(H11E,
 H11F), C12C(H12E,H12F), C5D(H5DA,H5DB), C6D(H6DA,H6DB), C7D(H7DA,H7DB),
 C8D(H8DA,H8DB), C9D(H9DA,H9DB), C10D(H10G,H10H), C11D(H11G,H11H), C12D(H12G,
 H12H), C5G(H5GA,H5GB), C6G(H6GA,H6GB), C7G(H7GA,H7GB), C8G(H8GA,H8GB),
 C9G(H9GA,H9GB), C10G(H10I,H10J), C11G(H11I,H11J), C12G(H12I,H12J)
8.b Aromatic/amide H refined with riding coordinates:
 N1D(H1D), N1E(H1E)
8.c Idealised Me refined as rotating group:
 C2A(H2AA,H2AB,H2AC), C3A(H3AA,H3AB,H3AC), C4A(H4AA,H4AB,H4AC), C2B(H2BA,H2BB,
 H2BC), C3B(H3BA,H3BB,H3BC), C4B(H4BA,H4BB,H4BC), C2C(H2CA,H2CB,H2CC), C3C(H3CA,
 H3CB,H3CC), C4C(H4CA,H4CB,H4CC), C2D(H2DA,H2DB,H2DC), C3D(H3DA,H3DB,H3DC),
 C4D(H4DA,H4DB,H4DC), C2G(H2GA,H2GB,H2GC), C3G(H3GA,H3GB,H3GC), C4G(H4GA,H4GB,
 H4GC)
;
_olex2_submission_special_instructions 'No special instructions were received'
_shelx_shelxl_version_number     2018/3
_diffrn_measurement_ambient_temperature_device_make 'Oxford Cryostream 800'
_shelx_res_checksum              4634