Synthesis, bonding properties and ether activation reactivity of cyclobutadienyl-ligated hybrid uranocenes
Tsoureas, Nikolaos; Mansikkamäki, Akseli; Layfield, Richard A.; Chemical Science 12 (2021) 2948–2954; doi:10.1039/D0SC05199C

data_1560036
_publ_section_title
;
 Synthesis, bonding properties and ether activation reactivity of
 cyclobutadienyl-ligated hybrid uranocenes
;
_journal_issue                   8
_journal_name_full               'Chemical Science'
_journal_page_first              2948
_journal_page_last               2954
_journal_paper_doi               10.1039/D0SC05199C
_journal_volume                  12
_journal_year                    2021
_chemical_formula_moiety         'C28 H52 O Si4 U'
_chemical_formula_sum            'C28 H52 O Si4 U'
_chemical_formula_weight         755.08
_chemical_name_common            2
_chemical_name_systematic        C28H52OSi4U
_chemical_properties_physical    Air-sensitive,Moisture-sensitive,Hygroscopic
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-11-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-12-11 deposited with the CCDC.	2021-01-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.40224(11)
_cell_length_b                   16.98119(18)
_cell_length_c                   17.03377(15)
_cell_measurement_reflns_used    26855
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      70.5970
_cell_measurement_theta_min      3.6360
_cell_volume                     3298.14(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1033
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -20.00  44.00   1.00    1.00    --    0.00 -99.00  90.00   64
  2  \w    -33.00  -6.00   1.00    2.50    --   14.00 105.00  54.54   27
  3  \w    -33.00  -7.00   1.00    2.50    --   14.00 106.00 147.87   26
  4  \w    -24.00   2.00   1.00    2.50    --   18.00  96.00 115.31   26
  5  \w    -15.00  14.00   1.00    2.50    --   22.00  87.00 -47.25   29
  6  \w     15.00 117.00   1.00    5.00    --   46.00  76.00-165.76  102
  7  \w     33.00 124.00   1.00    5.00    --   54.75  57.00  60.00   91
  8  \w      1.00  87.00   1.00    5.00    --   54.75-125.00 150.00   86
  9  \w     76.00 127.00   1.00    5.00    --   54.75 125.00-180.00   51
 10  \w     80.00 126.00   1.00    5.00    --   54.75  77.00 -60.00   46
 11  \w     76.00 127.00   1.00    5.00    --   54.75 125.00  30.00   51
 12  \w     76.00 127.00   1.00    5.00    --   54.75 125.00 120.00   51
 13  \w     76.00 127.00   1.00    5.00    --   54.75 125.00 -30.00   51
 14  \w     27.00 129.00   1.00    5.00    --   58.00  76.00   0.18  102
 15  \w     82.00 178.00   1.00   15.00    --  109.50  38.00 120.00   96
 16  \w     36.00  84.00   1.00   15.00    --  109.50-111.00 120.00   48
 17  \w     39.00 130.00   1.00   15.00    --  109.50 178.00 120.00   91
 18  \w     85.00 177.00   1.00   15.00    --  109.50  64.00 -30.00   92
 19  \w     83.00 178.00   1.00   15.00    --  109.50 111.00-180.00   95
 20  \w     80.00 178.00   1.00   15.00    --  109.50  77.00 -60.00   98
 21  \w     85.00 177.00   1.00   15.00    --  109.50  64.00  30.00   92
 22  \w     36.00  84.00   1.00   15.00    --  109.50-111.00-150.00   48
 23  \w     86.00 178.00   1.00   15.00    --  109.50  50.00-180.00   92
 24  \w     82.00 178.00   1.00   15.00    --  109.50  38.00 150.00   96
 25  \w     85.00 177.00   1.00   15.00    --  109.50  64.00-120.00   92
 26  \w     86.00 178.00   1.00   15.00    --  109.50  50.00   0.00   92
 27  \w     80.00 178.00   1.00   15.00    --  109.50  77.00   0.00   98
 28  \w     80.00 178.00   1.00   15.00    --  109.50  77.00   0.00   98
 29  \w     36.00  84.00   1.00   15.00    --  109.50-111.00-120.00   48
 30  \w     82.00 178.00   1.00   15.00    --  109.50  38.00 -60.00   96
 31  \w     80.00 178.00   1.00   15.00    --  109.50  77.00  30.00   98
 32  \w     39.00 133.00   1.00   15.00    --  109.50 -50.00-120.00   94
 33  \w     36.00  84.00   1.00   15.00    --  109.50-111.00-180.00   48
 34  \w    -16.00  13.00   1.00    2.50    --   22.00  88.00  19.57   29
 35  \w     -8.00  22.00   1.00    2.50    --   26.00  82.00 -13.21   30
 36  \w     -8.00  22.00   1.00    2.50    --   26.00  82.00-170.57   30
 37  \w     24.00 117.00   1.00    5.00    --   54.75  76.00 117.00   93
 38  \w     33.00 124.00   1.00    5.00    --   54.75  57.00 -90.00   91
 39  \w    -16.00  11.00   1.00    2.50    --    0.00 -99.00 -90.00   27
 40  \w    -22.00   4.00   1.00    2.50    --    0.00  77.00 -90.00   26
 41  \w    -18.00  21.00   1.00    2.50    --    0.00 -99.00   0.00   39
 42  \w     13.00  42.00   1.00    2.50    --    0.00 -99.00 -90.00   29
 43  \w    -83.00 -57.00   1.00    5.00    --  -54.75   0.00  60.00   26
 44  \w    -16.00  15.00   1.00    5.00    --  -54.75   0.00  60.00   31
 45  \w     92.00 118.00   1.00    5.00    --   54.75  77.00  30.00   26
 46  \w     44.00  70.00   1.00    5.00    --   54.75-125.00  60.00   26
 47  \w     81.00 107.00   1.00   15.00    --  109.50  77.00  90.00   26
 48  \w     54.00  85.00   1.00   15.00    --  109.50 -50.00   0.00   31
 49  \w     83.00 135.00   1.00   15.00    --  109.50 -77.00   0.00   52
 50  \w     88.00 115.00   1.00   15.00    --  109.50 -50.00   0.00   27
 51  \w     85.00 111.00   1.00   15.00    --  109.50  64.00-150.00   26
 52  \w     51.00  90.00   1.00   15.00    --  109.50 -77.00-150.00   39
 53  \w     81.00 107.00   1.00   15.00    --  109.50  25.00 -90.00   26
 54  \w    144.00 170.00   1.00   15.00    --  109.50  25.00-120.00   26
 55  \w     87.00 130.00   1.00   15.00    --  109.50  64.00  60.00   43
 56  \w    114.00 123.00   1.00   15.00    --  109.50 -25.00 -30.00    9
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0726514000
_diffrn_orient_matrix_UB_12      -0.0622534000
_diffrn_orient_matrix_UB_13      0.0443567000
_diffrn_orient_matrix_UB_21      -0.0991889000
_diffrn_orient_matrix_UB_22      -0.0085727000
_diffrn_orient_matrix_UB_23      0.0608081000
_diffrn_orient_matrix_UB_31      -0.0559665000
_diffrn_orient_matrix_UB_32      -0.0654658000
_diffrn_orient_matrix_UB_33      -0.0501301000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0963
_diffrn_reflns_av_unetI/netI     0.0480
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            43707
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.749
_diffrn_reflns_theta_min         3.675
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    15.371
_exptl_absorpt_correction_T_max  0.392
_exptl_absorpt_correction_T_min  0.145
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.71a (Rigaku Oxford Diffraction, 2020)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark brown'
_exptl_crystal_density_diffrn    1.521
_exptl_crystal_description       block
_exptl_crystal_F_000             1504
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: n-heptane'
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.095
_exptl_crystal_size_min          0.082
_refine_diff_density_max         0.942
_refine_diff_density_min         -1.185
_refine_diff_density_rms         0.122
_refine_ls_abs_structure_details
;
 Flack x determined using 2651 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.030(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     516
_refine_ls_number_reflns         6302
_refine_ls_number_restraints     115
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0281
_refine_ls_R_factor_gt           0.0273
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0380P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0641
_refine_ls_wR_factor_ref         0.0647
_reflns_Friedel_coverage         0.782
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                6162
_reflns_number_total             6302
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc05199c2.cif
_cod_data_source_block           C28H52OSi4U
_cod_depositor_comments
'Adding full bibliography for 1560031--1560036.cif.'
_cod_original_cell_volume        3298.14(5)
_cod_database_code               1560036
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C28 H48 O1 Si4 U'
_shelx_estimated_absorpt_t_max   0.365
_shelx_estimated_absorpt_t_min   0.168
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C28-C27 \\sim C26-C27
 with sigma of 0.02
 C25-C26 \\sim C25A-C26A
 with sigma of 0.02
 C25-O1 \\sim C25A-O1
 with sigma of 0.02
 C27-C28 \\sim C27A-C28A
 with sigma of 0.02
 C27-C26 \\sim C27A-C26A
 with sigma of 0.02
 C28-O1 \\sim C28A-O1
 with sigma of 0.02
 C25-C27 \\sim C25A-C27A
 with sigma of 0.04
 C27-O1 \\sim C27A-O1
 with sigma of 0.04
 C28-C26 \\sim C28A-C26A
 with sigma of 0.04
 C26-O1 \\sim C26A-O1
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C9) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.02
Uanis(C6) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C3AA) \\sim Ueq, Uanis(C4AA) \\sim Ueq, Uanis(C0AA) \\sim Ueq,
Uanis(C2AA) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C7AA) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.01
Uanis(C9AA) \\sim Ueq, Uanis(C1AA) \\sim Ueq, Uanis(C0BA) \\sim Ueq,
Uanis(C5AA) \\sim Ueq, Uanis(C1BA) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.005
Uanis(C25A) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C26A) \\sim Ueq, Uanis(C26)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
4. Others
 Sof(Si3A)=Sof(C8AA)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=Sof(C6AA)=Sof(H6AA)=
 Sof(H6AB)=Sof(H6AC)=Sof(C7AA)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=1-FVAR(1)
 Sof(Si3)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C19)=Sof(H19A)=Sof(H19B)=
 Sof(H19C)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(1)
 Sof(Si1A)=Sof(C1BA)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=Sof(C9AA)=Sof(H9AA)=
 Sof(H9AB)=Sof(H9AC)=Sof(C0BA)=Sof(H0BA)=Sof(H0BB)=Sof(H0BC)=1-FVAR(2)
 Sof(Si1)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C15)=Sof(H15A)=Sof(H15B)=
 Sof(H15C)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(2)
 Sof(C5AA)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=Sof(C3AA)=Sof(H3AA)=Sof(H3AB)=
 Sof(H3AC)=Sof(C4AA)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=Sof(Si2A)=1-FVAR(3)
 Sof(Si2)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C22)=Sof(H22A)=Sof(H22B)=
 Sof(H22C)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(3)
 Sof(Si4A)=Sof(C1AA)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C0AA)=Sof(H0AA)=
 Sof(H0AB)=Sof(H0AC)=Sof(C2AA)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=1-FVAR(4)
 Sof(Si4)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C16)=Sof(H16A)=Sof(H16B)=
 Sof(H16C)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=FVAR(4)
 Sof(C25A)=Sof(H25C)=Sof(H25D)=Sof(C26A)=Sof(H26C)=Sof(H26D)=Sof(C27A)=
 Sof(H27C)=Sof(H27D)=Sof(C28A)=Sof(H28C)=Sof(H28D)=1-FVAR(5)
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(C28)=Sof(H28A)=
 Sof(H28B)=Sof(C26)=Sof(H26A)=Sof(H26B)=FVAR(5)
5.a Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C27(H27A,H27B), C28(H28A,H28B), C26(H26A,H26B), C25A(H25C,
 H25D), C26A(H26C,H26D), C27A(H27C,H27D), C28A(H28C,H28D)
5.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C11(H11), C10(H10), C7(H7), C6(H6), C5(H5), C8(H8), C9(H9)
5.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C23(H23A,H23B,
 H23C), C22(H22A,H22B,H22C), C24(H24A,H24B,H24C), C21(H21A,H21B,H21C), C19(H19A,
 H19B,H19C), C20(H20A,H20B,H20C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C),
 C14(H14A,H14B,H14C), C5AA(H5AA,H5AB,H5AC), C3AA(H3AA,H3AB,H3AC), C4AA(H4AA,
 H4AB,H4AC), C1AA(H1AA,H1AB,H1AC), C0AA(H0AA,H0AB,H0AC), C2AA(H2AA,H2AB,H2AC),
 C8AA(H8AA,H8AB,H8AC), C6AA(H6AA,H6AB,H6AC), C7AA(H7AA,H7AB,H7AC), C1BA(H1BA,
 H1BB,H1BC), C9AA(H9AA,H9AB,H9AC), C0BA(H0BA,H0BB,H0BC)
;
_shelx_res_checksum              69031
_olex2_date_sample_data_collection 2020-11-24
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.642
_oxdiff_exptl_absorpt_empirical_full_min 0.422