Uranium(iv) alkyl cations: synthesis, structures, comparison with thorium(iv) analogues, and the influence of arene-coordination on thermal stability and ethylene polymerization activity
Andreychuk, Nicholas R.; Vidjayacoumar, Balamurugan; Price, Jeffrey S.; Kervazo, Sophie; Peeples, Craig A.; Emslie, David J. H.; Vallet, Valérie; Gomes, André S. P.; Réal, Florent; Schreckenbach, Georg; Ayers, Paul W.; Vargas-Baca, Ignacio; Jenkins, Hilary A.; Britten, James F.; Chemical Science  (2022) –; doi:10.1039/D2SC04302E

data_1567951
_publ_section_title
;
 Uranium(iv) alkyl cations: synthesis, structures, comparison with
 thorium(iv) analogues, and the influence of arene-coordination on thermal
 stability and ethylene polymerization activity
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC04302E
_journal_year                    2022
_chemical_formula_moiety         'C57 H79 N2 O Si U, B C24 F20, 2(C6 H6)'
_chemical_formula_sum            'C93 H91 B F20 N2 O Si U'
_chemical_formula_weight         1909.60
_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     direct
_audit_creation_date             2022-05-15
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-08-03 deposited with the CCDC.	2022-11-01 downloaded from the CCDC.
;
_cell_angle_alpha                95.996(3)
_cell_angle_beta                 111.194(3)
_cell_angle_gamma                95.687(3)
_cell_formula_units_Z            2
_cell_length_a                   13.916(3)
_cell_length_b                   17.437(4)
_cell_length_c                   19.155(4)
_cell_measurement_reflns_used    9961
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      23.06
_cell_measurement_theta_min      2.26
_cell_volume                     4262.7(16)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      150.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_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  0.0380
_diffrn_reflns_av_unetI/netI     0.0380
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            65558
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.521
_diffrn_reflns_theta_min         1.525
_exptl_absorpt_coefficient_mu    2.010
_exptl_absorpt_correction_T_max  0.9964
_exptl_absorpt_correction_T_min  0.5765
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.488
_exptl_crystal_description       plate
_exptl_crystal_F_000             1924
_exptl_crystal_size_max          0.458
_exptl_crystal_size_mid          0.356
_exptl_crystal_size_min          0.024
_refine_diff_density_max         0.892
_refine_diff_density_min         -0.733
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1123
_refine_ls_number_reflns         17563
_refine_ls_number_restraints     164
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0404
_refine_ls_R_factor_gt           0.0289
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0341P)^2^+2.4635P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0639
_refine_ls_wR_factor_ref         0.0675
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15069
_reflns_number_total             17563
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04302e2.cif
_cod_data_source_block           XA2_U_R_PhH_cation
_cod_original_cell_volume        4262.7(15)
_cod_database_code               1567951
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.953
_shelx_estimated_absorpt_t_min   0.460
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C17-C16 \\sim C18-C16 \\sim C19-C16 \\sim C17A-C16 \\sim C18A-C16 \\sim
C19A-C16 \\sim C17B-C16 ~
 C18B-C16 \\sim C19B-C16
 with sigma of 0.003
 C17-C18 \\sim C18-C19 \\sim C19-C17 \\sim C17A-C18A \\sim C18A-C19A \\sim
C19A-C17A \\sim C17B-C18B ~
 C18B-C19B \\sim C19B-C17B
 with sigma of 0.003
 C21-C20 \\sim C22-C20 \\sim C23-C20 \\sim C21A-C20 \\sim C22A-C20 \\sim
C23A-C20 \\sim C21B-C20 ~
 C22B-C20 \\sim C23B-C20
 with sigma of 0.003
 C21-C22 \\sim C22-C23 \\sim C23-C21 \\sim C21A-C22A \\sim C22A-C23A \\sim
C23A-C21A \\sim C21B-C22B ~
 C22B-C23B \\sim C23B-C21B
 with sigma of 0.003
3. Uiso/Uaniso restraints and constraints
Uanis(C18B) = Uanis(C17)
Uanis(C19) = Uanis(C18A)
Uanis(C19A) = Uanis(C17B)
Uanis(C18A) = Uanis(C19B)
Uanis(C18) = Uanis(C17A)
Uanis(C19) = Uanis(C18) = Uanis(C17)
Uanis(C18B) = Uanis(C17B) = Uanis(C19B)
Uanis(C19A) = Uanis(C18A) = Uanis(C17A)
Uanis(C22A) = Uanis(C23B) = Uanis(C23A) = Uanis(C22) = Uanis(C21A)
Uanis(C23) = Uanis(C21B)
Uanis(C22B) = Uanis(C21)
4. Rigid body (RIGU) restrains
 C37, C45, C47, C46
 with sigma for 1-2 distances of 0.0004 and sigma for 1-3 distances of 0.0004
5. Others
 1*[Sof(C17)+Sof(H17D)+Sof(H17E)+Sof(H17F)+Sof(C18)+Sof(H18D)+Sof(H18E)+
 Sof(H18F)+Sof(C19)+Sof(H19D)+Sof(H19E)+Sof(H19F)]+1*[Sof(C17A)+Sof(H17A)+
 Sof(H17B)+Sof(H17C)+Sof(C18A)+Sof(H18A)+Sof(H18B)+Sof(H18C)+Sof(C19A)+
 Sof(H19A)+Sof(H19B)+Sof(H19C)]+1*[Sof(C17B)+Sof(H17G)+Sof(H17H)+Sof(H17I)+
 Sof(C18B)+Sof(H18G)+Sof(H18H)+Sof(H18I)+Sof(C19B)+Sof(H19G)+Sof(H19H)+
 Sof(H19I)]=1 with esd of 0.00001
 1*[Sof(C21)+Sof(H21A)+Sof(H21B)+Sof(H21C)+Sof(C22)+Sof(H22A)+Sof(H22B)+
 Sof(H22C)+Sof(C23)+Sof(H23A)+Sof(H23B)+Sof(H23C)]+1*[Sof(C21A)+Sof(H21D)+
 Sof(H21E)+Sof(H21F)+Sof(C22A)+Sof(H22D)+Sof(H22E)+Sof(H22F)+Sof(C23A)+
 Sof(H23D)+Sof(H23E)+Sof(H23F)]+1*[Sof(C21B)+Sof(H21G)+Sof(H21H)+Sof(H21I)+
 Sof(C22B)+Sof(H22G)+Sof(H22H)+Sof(H22I)+Sof(C23B)+Sof(H23G)+Sof(H23H)+
 Sof(H23I)]=1 with esd of 0.00001
 Sof(C17)=Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(C18)=Sof(H18D)=Sof(H18E)=Sof(H18F)=
 Sof(C19)=Sof(H19D)=Sof(H19E)=Sof(H19F)=FVAR(1)
 Sof(C17A)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18A)=Sof(H18A)=Sof(H18B)=
 Sof(H18C)=Sof(C19A)=Sof(H19A)=Sof(H19B)=Sof(H19C)=FVAR(2)
 Sof(C17B)=Sof(H17G)=Sof(H17H)=Sof(H17I)=Sof(C18B)=Sof(H18G)=Sof(H18H)=
 Sof(H18I)=Sof(C19B)=Sof(H19G)=Sof(H19H)=Sof(H19I)=FVAR(3)
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(4)
 Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C22A)=Sof(H22D)=Sof(H22E)=
 Sof(H22F)=Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=FVAR(5)
 Sof(C21B)=Sof(H21G)=Sof(H21H)=Sof(H21I)=Sof(C22B)=Sof(H22G)=Sof(H22H)=
 Sof(H22I)=Sof(C23B)=Sof(H23G)=Sof(H23H)=Sof(H23I)=FVAR(6)
6.a Ternary CH refined with riding coordinates:
 C30(H30), C33(H33), C42(H42), C45(H45)
6.b Me refined with riding coordinates:
 C17A(H17A,H17B,H17C), C18A(H18A,H18B,H18C), C19A(H19A,H19B,H19C), C21(H21A,
 H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C17(H17D,H17E,H17F),
 C18(H18D,H18E,H18F), C19(H19D,H19E,H19F), C21A(H21D,H21E,H21F), C22A(H22D,H22E,
 H22F), C23A(H23D,H23E,H23F), C17B(H17G,H17H,H17I), C18B(H18G,H18H,H18I),
 C19B(H19G,H19H,H19I), C21B(H21G,H21H,H21I), C22B(H22G,H22H,H22I), C23B(H23G,
 H23H,H23I)
6.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C6(H6), C8(H8), C26(H26), C27(H27), C28(H28), C38(H38),
 C39(H39), C40(H40), C52(H52), C53(H53), C54(H54), C55(H55), C56(H56), C57(H57),
  C82(H82), C83(H83), C84(H84), C85(H85), C86(H86), C87(H87), C88(H88),
 C89(H89), C90(H90), C91(H91), C92(H92), C93(H93)
6.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C31(H31A,H31B,H31C), C32(H32A,H32B,
 H32C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C43(H43A,H43B,H43C), C44(H44A,
 H44B,H44C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C49(H49A,H49B,H49C),
 C50(H50A,H50B,H50C), C51(H51A,H51B,H51C)
;
_shelx_res_checksum              19099
_olex2_submission_special_instructions 'No special instructions were received'