Spectroscopic and Electrochemical Characterization of a Pr4+ Imidophosphorane Complex and the Redox Chemistry of Nd3+ and Dy3+ Complexes
Rice, Natalie T.; Popov, Ivan A.; Carlson, Rebbeca; Greer, Samuel M.; Boggiano, Andrew C.; Stein, Benjamin William; Bacsa, John; Batista, Enrique R.; Yang, Ping; La Pierre, Henry Storms; Dalton Transactions  (2022) –; doi:10.1039/D2DT00758D

data_7709922
_publ_section_title
;
 Spectroscopic and Electrochemical Characterization of a Pr4+
 Imidophosphorane Complex and the Redox Chemistry of Nd3+ and Dy3+
 Complexes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT00758D
_journal_year                    2022
_chemical_formula_moiety         'C56 H128 N16 P4 Pr, K'
_chemical_formula_sum            'C56 H128 K N16 P4 Pr'
_chemical_formula_weight         1329.63
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-09-27
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_audit_update_record
;
2021-10-07 deposited with the CCDC.	2022-04-01 downloaded from the CCDC.
;
_cell_angle_alpha                75.191(4)
_cell_angle_beta                 81.487(4)
_cell_angle_gamma                65.497(4)
_cell_formula_units_Z            2
_cell_length_a                   13.0693(16)
_cell_length_b                   13.9895(17)
_cell_length_c                   23.626(3)
_cell_measurement_reflns_used    9620
_cell_measurement_temperature    108.93
_cell_measurement_theta_max      30.42
_cell_measurement_theta_min      2.53
_cell_volume                     3795.7(8)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2016)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2016)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      108.93
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.993
_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  0.0677
_diffrn_reflns_av_unetI/netI     0.0704
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            81875
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.575
_diffrn_reflns_theta_min         2.232
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.823
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6420
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1049 before and 0.0762 after correction.
The Ratio of minimum to maximum transmission is 0.8605.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.163
_exptl_crystal_description       plate
_exptl_crystal_F_000             1428
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.414
_exptl_crystal_size_mid          0.244
_exptl_crystal_size_min          0.104
_refine_diff_density_max         1.543
_refine_diff_density_min         -1.363
_refine_diff_density_rms         0.120
_refine_ls_extinction_coef       0.00181(18)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1043
_refine_ls_number_reflns         23153
_refine_ls_number_restraints     2032
_refine_ls_restrained_S_all      1.173
_refine_ls_R_factor_all          0.0658
_refine_ls_R_factor_gt           0.0555
_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^)+(0.0263P)^2^+12.4630P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1224
_refine_ls_wR_factor_ref         0.1271
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19832
_reflns_number_total             23153
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00758d2.cif
_cod_data_source_block           ntr-03-56-r
_cod_database_code               7709922
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.919
_shelx_estimated_absorpt_t_min   0.727
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Pr1-N1_5 \\sim Pr1-N1_6
 with sigma of 0.002
 Pr1-N1_8 \\sim Pr1-N1_7
 with sigma of 0.002
3. Uiso/Uaniso restraints and constraints
Uanis(N2_6) = Uanis(N2_5)
Uanis(N1_5) = Uanis(N1_6)
Uanis(N4_6) = Uanis(N4_5)
Uanis(C12_6) = Uanis(C12_5)
Uanis(C7_6) = Uanis(C7_5)
Uanis(C8_6) = Uanis(C8_5)
Uanis(C4_5) = Uanis(C4_6)
Uanis(C14_6) = Uanis(C14_5)
Uanis(C9_6) = Uanis(C9_5)
Uanis(C14_3) = Uanis(C14_4)
Uanis(C13_4) = Uanis(C13_3)
Uanis(C1_4) = Uanis(C1_3)
Uanis(N2_4) = Uanis(N2_3)
Uanis(N1_4) = Uanis(N1_3)
Uanis(C5_3) = Uanis(C5_4)
Uanis(C2_4) = Uanis(C2_3)
Uanis(N3_4) = Uanis(N3_3)
Uanis(N2_3) = Uanis(N2_4)
Uanis(C3_4) = Uanis(C3_3)
Uanis(C6_4) = Uanis(C6_3)
Uanis(C9_3) = Uanis(C9_4)
Uanis(N1_7) = Uanis(N1_8)
Uanis(N2_7) = Uanis(N2_8)
Uanis(C1_7) = Uanis(C1_8)
Uanis(C3_7) = Uanis(C3_8)
Uanis(P1_7) = Uanis(P1_8)
Uanis(C2_7) = Uanis(C2_8)
Uanis(C4_7) = Uanis(C4_8)
Uanis(C5_7) = Uanis(C5_8)
Uanis(C6_7) = Uanis(C6_8)
Uanis(N3_7) = Uanis(N3_8)
Uanis(N4_7) = Uanis(N4_8)
Uanis(C7_7) = Uanis(C7_8)
Uanis(C13_7) = Uanis(C13_8)
Uanis(C11_7) = Uanis(C11_8)
Uanis(C10_7) = Uanis(C10_8)
Uanis(C8_7) = Uanis(C8_8)
Uanis(C9_7) = Uanis(C9_8)
Uanis(C14_7) = Uanis(C14_8)
Uanis(C12_7) = Uanis(C12_8)
Uanis(K1B) = Uanis(K1A)
4. Rigid body (RIGU) restrains
 P1_1, N1_1, N2_1, N3_1, N4_1, C1_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1, C8_1,
 C9_1, C10_1, C11_1, C12_1, C13_1, C14_1
 P1_3, N1_3, N2_3, N3_3, N4_3, C1_3, C2_3, C3_3, C4_3, C5_3, C6_3, C7_3, C8_3,
 C9_3, C10_3, C11_3, C12_3, C13_3, C14_3
 P1_4, N1_4, N2_4, N3_4, N4_4, C1_4, C2_4, C3_4, C4_4, C5_4, C6_4, C7_4, C8_4,
 C9_4, C10_4, C11_4, C12_4, C13_4, C14_4
 P1_5, N1_5, N2_5, N3_5, N4_5, C1_5, C2_5, C3_5, C4_5, C5_5, C6_5, C7_5, C8_5,
 C9_5, C10_5, C11_5, C12_5, C13_5, C14_5
 P1_6, N1_6, N2_6, N3_6, N4_6, C1_6, C2_6, C3_6, C4_6, C5_6, C6_6, C7_6, C8_6,
 C9_6, C10_6, C11_6, C12_6, C13_6, C14_6
 P1_7, N1_7, N2_7, N3_7, N4_7, C1_7, C2_7, C3_7, C4_7, C5_7, C6_7, C7_7, C8_7,
 C9_7, C10_7, C11_7, C12_7, C13_7, C14_7
 P1_8, N1_8, N2_8, N3_8, N4_8, C1_8, C2_8, C3_8, C4_8, C5_8, C6_8, C7_8, C8_8,
 C9_8, C10_8, C11_8, C12_8, C13_8, C14_8
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0004
5. Same fragment restrains
{P1_3, N1_3, N2_3, N3_3, N4_3, C1_3, C2_3, C3_3, C4_3, C5_3, C6_3, C7_3, C8_3,
C9_3, C10_3, C11_3, C12_3, C13_3, C14_3}
{P1_4, N1_4, N2_4, N3_4, N4_4, C1_4, C2_4, C3_4, C4_4, C5_4, C6_4, C7_4, C8_4,
C9_4, C10_4, C11_4, C12_4, C13_4, C14_4}
{P1_5, N1_5, N2_5, N3_5, N4_5, C1_5, C2_5, C3_5, C4_5, C5_5, C6_5, C7_5, C8_5,
C9_5, C10_5, C11_5, C12_5, C13_5, C14_5}
{P1_6, N1_6, N2_6, N3_6, N4_6, C1_6, C2_6, C3_6, C4_6, C5_6, C6_6, C7_6, C8_6,
C9_6, C10_6, C11_6, C12_6, C13_6, C14_6}
{P1_7, N1_7, N2_7, N3_7, N4_7, C1_7, C2_7, C3_7, C4_7, C5_7, C6_7, C7_7, C8_7,
C9_7, C10_7, C11_7, C12_7, C13_7, C14_7}
{P1_8, N1_8, N2_8, N3_8, N4_8, C1_8, C2_8, C3_8, C4_8, C5_8, C6_8, C7_8, C8_8,
C9_8, C10_8, C11_8, C12_8, C13_8, C14_8}
as
{P1_1, N1_1, N2_1, N3_1, N4_1, C1_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1, C8_1,
C9_1, C10_1, C11_1, C12_1, C13_1, C14_1} sigma for 1-2: 0.002 1-3: 0.004
6. Others
 Sof(K1A)=Sof(P1)=Sof(N1)=Sof(N2)=Sof(N3)=Sof(N4)=Sof(C1)=Sof(H1A)=Sof(H1B)=
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C5)=
 Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C7)=Sof(C8)=
 Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=
 Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=
 Sof(H12B)=Sof(H12C)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=Sof(P1)=Sof(N1)=Sof(N2)=Sof(N3)=Sof(N4)=Sof(C1)=Sof(H1A)=Sof(H1B)=
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C5)=
 Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C7)=Sof(C8)=
 Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=
 Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=
 Sof(H12B)=Sof(H12C)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=Sof(P1)=Sof(N1)=Sof(N2)=Sof(N3)=Sof(N4)=Sof(C1)=Sof(H1A)=Sof(H1B)=
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C5)=
 Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C7)=Sof(C8)=
 Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=
 Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=
 Sof(H12B)=Sof(H12C)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=1-FVAR(1)
 Sof(K1B)=Sof(P1)=Sof(N1)=Sof(N2)=Sof(N3)=Sof(N4)=Sof(C1)=Sof(H1A)=Sof(H1B)=
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C5)=
 Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C7)=Sof(C8)=
 Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=
 Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=
 Sof(H12B)=Sof(H12C)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=Sof(P1)=Sof(N1)=Sof(N2)=Sof(N3)=Sof(N4)=Sof(C1)=Sof(H1A)=Sof(H1B)=
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C5)=
 Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C7)=Sof(C8)=
 Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=
 Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=
 Sof(H12B)=Sof(H12C)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=Sof(P1)=Sof(N1)=Sof(N2)=Sof(N3)=Sof(N4)=Sof(C1)=Sof(H1A)=Sof(H1B)=
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C5)=
 Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C7)=Sof(C8)=
 Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=
 Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=
 Sof(H12B)=Sof(H12C)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C11(H11A,H11B), C13(H13A,H13B), C1(H1A,H1B), C2(H2A,
 H2B), C11(H11A,H11B), C13(H13A,H13B), C1(H1A,H1B), C2(H2A,H2B), C11(H11A,H11B),
  C13(H13A,H13B), C1(H1A,H1B), C2(H2A,H2B), C11(H11A,H11B), C13(H13A,H13B),
 C1(H1A,H1B), C2(H2A,H2B), C11(H11A,H11B), C13(H13A,H13B), C1(H1A,H1B), C2(H2A,
 H2B), C11(H11A,H11B), C13(H13A,H13B), C1(H1A,H1B), C2(H2A,H2B), C11(H11A,H11B),
  C13(H13A,H13B)
7.b Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,
 H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C),
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,
 H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C4(H4A,
 H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C),
 C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C4(H4A,H4B,H4C),
  C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C4(H4A,H4B,H4C), C5(H5A,
 H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,
 H10C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C4(H4A,H4B,H4C), C5(H5A,H5B,
 H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C),
 C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C12(H12A,H12B,H12C), C14(H14A,H14B,H14C)
;
_smtbx_masks_void_probe_radius   0.3
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              19142
_shelx_hkl_checksum              67265
_shelx_fab_checksum              46939
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_special_instructions 'No special instructions were received'