Isolation of C1 through C4 derivatives from CO using heteroleptic uranium(iii) metallocene aryloxide complexes
Ward, Robert J.; Rosal, Iker del; Kelley, Steven P.; Maron, Laurent; Walensky, Justin R.; Chemical Science 14 (2023) 2024–2032; doi:10.1039/D2SC06375A

data_1568512
_publ_section_title
;
 Isolation of C1 through C4 derivatives from CO using heteroleptic
 uranium(iii) metallocene aryloxide complexes
;
_journal_issue                   8
_journal_name_full               'Chemical Science'
_journal_page_first              2024
_journal_page_last               2032
_journal_paper_doi               10.1039/D2SC06375A
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C60 H82 O6 S U2, 1.5(C7 H8)'
_chemical_formula_sum            'C70.5 H94 O6 S U2'
_chemical_formula_weight         1545.57
_chemical_properties_physical    Air-sensitive
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-11-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-11-16 deposited with the CCDC.	2023-01-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   56.6846(17)
_cell_length_b                   56.6846(17)
_cell_length_c                   10.2786(3)
_cell_measurement_reflns_used    8471
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      48.02
_cell_measurement_theta_min      2.70
_cell_volume                     28601.9(15)
_computing_cell_refinement       'Bruker Apex3 V.2016.9-0/SAINT V8.37A'
_computing_data_collection       'Bruker Apex3 V.2016.9-0'
_computing_data_reduction        'Bruker Apex3 V.2016.9-0/SAINT V8.37A'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1309
_diffrn_reflns_av_unetI/netI     0.0509
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       56
_diffrn_reflns_limit_h_min       -56
_diffrn_reflns_limit_k_max       56
_diffrn_reflns_limit_k_min       -56
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            115660
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        50.503
_diffrn_reflns_theta_max         50.503
_diffrn_reflns_theta_min         2.700
_diffrn_source                   'Sealed Source Mo with TRIUMPH optics'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    14.927
_exptl_absorpt_correction_T_max  0.7500
_exptl_absorpt_correction_T_min  0.4601
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Bruker AXScale'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.615
_exptl_crystal_description       prism
_exptl_crystal_F_000             13770
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         2.108
_refine_diff_density_min         -0.729
_refine_diff_density_rms         0.132
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     768
_refine_ls_number_reflns         6685
_refine_ls_number_restraints     1113
_refine_ls_restrained_S_all      0.944
_refine_ls_R_factor_all          0.0592
_refine_ls_R_factor_gt           0.0419
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0419P)^2^+929.3653P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0972
_refine_ls_wR_factor_ref         0.1058
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5414
_reflns_number_total             6685
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06375a3.cif
_cod_data_source_block           9
_cod_original_cell_volume        28601.9(19)
_cod_original_sg_symbol_H-M      'R -3'
_cod_original_formula_sum        'C70.50 H94 O6 S U2'
_cod_database_code               1568512
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.754
_shelx_estimated_absorpt_t_min   0.267
_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
 C34-C33 \\sim C32-C33 \\sim C35-C34 \\sim C35-C36 \\sim C32-C36
 with sigma of 0.02
 C46-C42 \\sim C42-C43 \\sim C44-C45 \\sim C46-C45 \\sim C43-C44
 with sigma of 0.02
 C42-C44 \\sim C45-C43 \\sim C46-C43 \\sim C42-C45
 with sigma of 0.02
 C49'-C50' \\sim C51'-C47' \\sim C47'-C48' \\sim C50'-C51'
 with sigma of 0.02
 C45'-C44' \\sim C45'-C46' \\sim C42'-C46' \\sim C42'-C43' \\sim C44'-C43'
 with sigma of 0.02
 C44'-C49' \\sim C45'-C50' \\sim C51'-C46' \\sim C42'-C47' \\sim C48'-C43'
 with sigma of 0.02
 C39'-C34' \\sim C40'-C35' \\sim C41'-C36' \\sim C37'-C32' \\sim C38'-C33'
 with sigma of 0.02
 C34'-C35' \\sim C36'-C35' \\sim C36'-C32' \\sim C32'-C33' \\sim C33'-C34'
 with sigma of 0.02
 C34'-C36' \\sim C35'-C33' \\sim C32'-C34' \\sim C33'-C36'
 with sigma of 0.02
 C40'-C41' \\sim C37'-C38' \\sim C39'-C40' \\sim C41'-C37'
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Fixed Sof: C32(0.667) C32'(0.333) C33(0.667) C33'(0.333) C34(0.667)
 C34'(0.333) C35(0.667) C35'(0.333) C36(0.667) C36'(0.333) C37(0.667)
 H37A(0.667) H37B(0.667) H37C(0.667) C37'(0.333) H37D(0.333) H37E(0.333)
 H37F(0.333) C38(0.667) H38A(0.667) H38B(0.667) H38C(0.667) C38'(0.333)
 H38D(0.333) H38E(0.333) H38F(0.333) C39(0.667) H39A(0.667) H39B(0.667)
 H39C(0.667) C39'(0.333) H39D(0.333) H39E(0.333) H39F(0.333) C40(0.667)
 H40A(0.667) H40B(0.667) H40C(0.667) C40'(0.333) H40D(0.333) H40E(0.333)
 H40F(0.333) C41(0.667) H41A(0.667) H41B(0.667) H41C(0.667) C41'(0.333)
 H41D(0.333) H41E(0.333) H41F(0.333) C42(0.5) C42'(0.5) C43(0.5) C43'(0.5)
 C44(0.5) C44'(0.5) C45(0.5) C45'(0.5) C46(0.5) C46'(0.5) C47(0.5) H47A(0.5)
 H47B(0.5) H47C(0.5) C47'(0.5) H47D(0.5) H47E(0.5) H47F(0.5) C48(0.5) H48A(0.5)
 H48B(0.5) H48C(0.5) C48'(0.5) H48D(0.5) H48E(0.5) H48F(0.5) C49(0.5) H49A(0.5)
 H49B(0.5) H49C(0.5) C49'(0.5) H49D(0.5) H49E(0.5) H49F(0.5) C50(0.5) H50A(0.5)
 H50B(0.5) H50C(0.5) C50'(0.5) H50D(0.5) H50E(0.5) H50F(0.5) C51(0.5) H51A(0.5)
 H51B(0.5) H51C(0.5) C51'(0.5) H51D(0.5) H51E(0.5) H51F(0.5)
5.a Me refined with riding coordinates:
 C47(H47A,H47B,H47C), C47'(H47D,H47E,H47F), C48(H48A,H48B,H48C), C48'(H48D,
 H48E,H48F), C49(H49A,H49B,H49C), C49'(H49D,H49E,H49F), C50(H50A,H50B,H50C),
 C50'(H50D,H50E,H50F), C51(H51A,H51B,H51C), C51'(H51D,H51E,H51F)
5.b Aromatic/amide H refined with riding coordinates:
 C23(H23), C25(H25), C54(H54), C56(H56)
5.c Idealised Me refined with riding coordinates:
 C37(H37A,H37B,H37C), C37'(H37D,H37E,H37F), C38(H38A,H38B,H38C), C38'(H38D,
 H38E,H38F), C39(H39A,H39B,H39C), C39'(H39D,H39E,H39F), C40(H40A,H40B,H40C),
 C40'(H40D,H40E,H40F), C41(H41A,H41B,H41C), C41'(H41D,H41E,H41F)
5.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C), C29(H29A,H29B,H29C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,
 H60B,H60C)
;
_shelx_res_checksum              42737
_shelx_hkl_checksum              66542
_shelx_fab_checksum              23895
_olex2_submission_special_instructions 'No special instructions were received'