Extreme π-Loading as a Design Element for Accessing Imido Ligand Reactivity. A CCC-NHC Pincer Tantalum Bis(imido) Complex: Synthesis, Characterization, and Catalytic Oxidative Amination of Alkenes
Helgert, Theodore R.; Zhang, Xiaofei; Box, Hannah K.; Denny, Jason A.; Valle, Henry U.; Oliver, Allen G.; Akurathi, Gopalakrishna; Webster, Charles Edwin; Hollis, T. Keith; Organometallics 35 (2016) 3452–; doi:10.1021/acs.organomet.6b00216

data_4088584
_publ_section_title
;
 Extreme \p-Loading as a Design Element for Accessing Imido Ligand
 Reactivity. A CCC-NHC Pincer Tantalum Bis(imido) Complex: Synthesis,
 Characterization, and Catalytic Oxidative Amination of Alkenes
;
_journal_issue                   20
_journal_name_full               Organometallics
_journal_page_first              3452
_journal_paper_doi               10.1021/acs.organomet.6b00216
_journal_volume                  35
_journal_year                    2016
_chemical_formula_moiety         'C28 H43 I Li N6 Ta'
_chemical_formula_sum            'C28 H43 I Li N6 Ta'
_chemical_formula_weight         778.47
_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     direct
_audit_creation_date             2016-05-17
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2016-05-18 # Formatted by publCIF

;
_cell_angle_alpha                96.432(2)
_cell_angle_beta                 92.191(2)
_cell_angle_gamma                117.377(2)
_cell_formula_units_Z            2
_cell_length_a                   10.4676(5)
_cell_length_b                   11.0982(5)
_cell_length_c                   15.7331(8)
_cell_measurement_reflns_used    9964
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      27.66
_cell_measurement_theta_min      2.30
_cell_volume                     1604.45(14)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0499
_diffrn_reflns_av_unetI/netI     0.0399
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            39862
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.281
_diffrn_reflns_theta_min         2.089
_exptl_absorpt_coefficient_mu    4.413
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.4746
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/2 (Bruker,2014/2) was used for absorption correction.
wR2(int) was 0.1033 before and 0.0592 after correction.
The Ratio of minimum to maximum transmission is 0.6365.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.611
_exptl_crystal_description       Plate
_exptl_crystal_F_000             764
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.739
_refine_diff_density_min         -2.022
_refine_diff_density_rms         0.172
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     355
_refine_ls_number_reflns         7885
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0558
_refine_ls_R_factor_gt           0.0448
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0378P)^2^+11.9597P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1014
_refine_ls_wR_factor_ref         0.1073
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6775
_reflns_number_total             7885
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00216_si_002.cif
_cod_data_source_block           tri
_cod_database_code               4088584
_shelx_estimated_absorpt_t_max   0.810
_shelx_estimated_absorpt_t_min   0.351
_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
 C22-C23 \\sim C23-C24 \\sim C24-C22 \\sim C22A-C23A \\sim C23A-C24A \\sim
C24A-C22A
 with sigma of 0.02
 C21-C22 \\sim C21-C23 \\sim C21-C24 \\sim C21-C22A \\sim C21-C23A \\sim
C21-C24A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C22) = Uanis(C22A)
Uanis(C23) = Uanis(C23A)
Uanis(C24) = Uanis(C24A)
4. Others
 Sof(C22A)=Sof(H22D)=Sof(H22E)=Sof(H22F)=Sof(C23A)=Sof(H23D)=Sof(H23E)=
 Sof(H23F)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=1-FVAR(1)
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C17(H17A,H17B), C18(H18A,H18B),
 C19(H19A,H19B)
5.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C14(H14), C15(H15)
5.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C22A(H22D,H22E,
 H22F), C23(H23A,H23B,H23C), C23A(H23D,H23E,H23F), C24(H24A,H24B,H24C),
 C24A(H24D,H24E,H24F), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'