Synthesis of a Uranium(VI)-Carbene: Reductive Formation of Uranyl(V)-Methanides, Oxidative Preparation of a [R2C=U=O]2+ Analogue of the [O=U=O]2+ Uranyl Ion (R = Ph2PNSiMe3), and Comparison of the Nature of UIV=C, UV=C, and UVI=C Double Bonds
David P. Mills; Oliver J. Cooper; Floriana Tuna; Eric J. L. McInnes; E. Stephen Davies; Jonathan McMaster; Fabrizio Moro; William Lewis; Alexander J. Blake; Stephen T. Liddle; Journal of the American Chemical Society 134 (2012) 10047–10054; doi:10.1021/ja301333f

data_4118065
_publ_section_title
;
 Synthesis of a Uranium(VI)-Carbene: Reductive Formation of
 Uranyl(V)-Methanides, Oxidative Preparation of a [R2C=U=O]2+ Analogue of
 the [O=U=O]2+ Uranyl Ion (R = Ph2PNSiMe3), and Comparison of the Nature
 of UIV=C, UV=C, and UVI=C Double Bonds
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10047
_journal_page_last               10054
_journal_paper_doi               10.1021/ja301333f
_journal_volume                  134
_journal_year                    2012
_chemical_formula_moiety         'C93 H115 Cl N6 O6 P6 Si6 U3, 4(C7 H8)'
_chemical_formula_sum            'C121 H147 Cl N6 O6 P6 Si6 U3'
_chemical_formula_weight         2885.35
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   'geom, Me from difmap'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           'enCIFer editing of SHELXL97 CIF output'
_cell_angle_alpha                90.00
_cell_angle_beta                 104.515(1)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   15.2550(8)
_cell_length_b                   28.8625(15)
_cell_length_c                   29.2694(15)
_cell_measurement_reflns_used    14016
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      27.43
_cell_measurement_theta_min      2.22
_cell_volume                     12475.9(11)
_computing_cell_refinement       'Bruker SAINT version 6.36A (Bruker, 2000)'
_computing_data_collection       'Bruker SMART version 5.625 (Bruker, 2001)'
_computing_data_reduction        'Bruker SAINT; SHELXTL (Sheldrick, 2008)'
_computing_molecular_graphics    'SHELXTL (Sheldrick, 2008)'
_computing_publication_material
'enCIFer (Allen et al., 2004); PLATON (Spek, 2009)'
_computing_structure_refinement  'SHELXL97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXTL (Sheldrick, 2008)'
_diffrn_ambient_temperature      90(2)
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker SMART APEX CCD diffractometer'
_diffrn_measurement_method       '\w rotation with narrow frames'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'normal-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.054
_diffrn_reflns_av_sigmaI/netI    0.067
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            78629
_diffrn_reflns_theta_full        27.55
_diffrn_reflns_theta_max         27.55
_diffrn_reflns_theta_min         1.97
_diffrn_standards_decay_%        0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.094
_exptl_absorpt_correction_T_max  0.3675
_exptl_absorpt_correction_T_min  0.2252
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   '(SADABS; Bruker, 2001)'
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.536
_exptl_crystal_description       block
_exptl_crystal_F_000             5720
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.14
_refine_diff_density_max         4.87
_refine_diff_density_min         -1.66
_refine_diff_density_rms         0.19
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.02
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1320
_refine_ls_number_reflns         28609
_refine_ls_number_restraints     8
_refine_ls_restrained_S_all      1.03
_refine_ls_R_factor_all          0.0722
_refine_ls_R_factor_gt           0.0480
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.068P)^2^+16.32P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.115
_refine_ls_wR_factor_ref         0.127
_reflns_number_gt                21586
_reflns_number_total             28609
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            ja301333f_si_001_2.cif
_cod_data_source_block           3
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               4118065