Synthesis of NPN-Coordinated Tantalum Alkyl Complexes and Their Hydrogenolysis: Isolation of a Terminal Tantalum Hydride Incorporating a Doubly Cyclometalated NPN Scaffold
Batke, Sonja; Sietzen, Malte; Wadepohl, Hubert; Ballmann, Joachim; Inorganic Chemistry  (2017) –; doi:10.1021/acs.inorgchem.7b00277

data_4345724
_publ_section_title
;
 Synthesis of NPN-Coordinated Tantalum Alkyl Complexes and Their
 Hydrogenolysis: Isolation of a Terminal Tantalum Hydride Incorporating a
 Doubly Cyclometalated NPN Scaffold
;
_journal_name_full               'Inorganic Chemistry'
_journal_paper_doi               10.1021/acs.inorgchem.7b00277
_journal_year                    2017
_chemical_formula_moiety         'C76 H68 F12 N4 O12 P2 S4 Ta2, 3(C7 H8)'
_chemical_formula_sum            'C97 H92 F12 N4 O12 P2 S4 Ta2'
_chemical_formula_weight         2285.82
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_cell_setting           triclinic
_symmetry_Int_Tables_number      2
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_block_code                ba_ms9
_audit_creation_date
;
'Fri Mar 28 10:25:40 2014'
;
_audit_creation_method
;
Olex2 1.2
(compiled Aug 23 2016 16:59:57 for OlexSys, GUI svn.r5221)
;
_audit_update_record
'05.09.2016 17:02:16 CEST UTC+02:00  encif 1.46'
_cell_angle_alpha                74.5788(15)
_cell_angle_beta                 89.5752(13)
_cell_angle_gamma                72.9103(16)
_cell_formula_units_Z            2
_cell_length_a                   13.8800(2)
_cell_length_b                   19.0045(4)
_cell_length_c                   20.1978(3)
_cell_measurement_reflns_used    23569
_cell_measurement_temperature    110(1)
_cell_measurement_theta_max      25.8160
_cell_measurement_theta_min      3.5390
_cell_volume                     4894.75(16)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material
'encif (Wadepohl, 2009-15); encifer 1.5 (CCDC, 2014)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2013)'
_diffrn_ambient_environment      'perfluoro polyether oil / N~2~'
_diffrn_ambient_temperature      110(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega  -50.00   25.00   0.5000   14.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.5380   79.0000  -85.4235 150

  2 omega   -3.00   86.00   0.5000   14.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161   57.0000   60.0000 178

  3 omega   -6.00   83.00   0.5000   14.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161   77.0000  120.0000 178

  4 omega    4.00   86.00   0.5000   14.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161   57.0000 -120.0000 164

  5 omega  -44.00   50.00   0.5000   14.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -80.0000   -6.3506 188

  6 omega    3.00   85.00   0.5000   14.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161   57.0000  -30.0000 164

  7 omega  -39.00   49.00   0.5000   14.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -77.0000 -180.0000 176

  8 omega  -43.00   45.00   0.5000   14.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -79.0000   98.5202 176

  9 omega   -7.00   91.00   0.5000   14.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161   38.0000 -180.0000 196

 10 omega  -50.00   40.00   0.5000   14.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -57.0000    0.0000 180

 11 omega  -11.00   89.00   0.5000   14.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161   77.0000  -60.0000 200

 12 omega  -50.00   40.00   0.5000   14.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -57.0000 -180.0000 180

 13 omega   -3.00   87.00   0.5000   14.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161   57.0000   90.0000 180

 14 omega  -52.00   49.00   0.5000   14.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -77.0000  120.0000 202

;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_UB_11      0.0154162000
_diffrn_orient_matrix_UB_12      -0.0405941000
_diffrn_orient_matrix_UB_13      0.0088525000
_diffrn_orient_matrix_UB_21      0.0513542000
_diffrn_orient_matrix_UB_22      -0.0006736000
_diffrn_orient_matrix_UB_23      0.0006615000
_diffrn_orient_matrix_UB_31      -0.0005659000
_diffrn_orient_matrix_UB_32      -0.0014035000
_diffrn_orient_matrix_UB_33      0.0354421000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0872
_diffrn_reflns_av_unetI/netI     0.0633
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            117387
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.398
_diffrn_reflns_theta_min         3.253
_diffrn_source                   'microfocus X-Ray tube'
_exptl_absorpt_coefficient_mu    2.436
_exptl_absorpt_correction_T_max  0.910
_exptl_absorpt_correction_T_min  0.639
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.551
_exptl_crystal_description       plate
_exptl_crystal_F_000             2292
_exptl_crystal_size_max          0.246
_exptl_crystal_size_mid          0.078
_exptl_crystal_size_min          0.040
_refine_diff_density_max         7.133
_refine_diff_density_min         -2.013
_refine_diff_density_rms         0.155
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1212
_refine_ls_number_reflns         20043
_refine_ls_number_restraints     180
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0682
_refine_ls_R_factor_gt           0.0525
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0387P)^2^+33.2348P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1116
_refine_ls_wR_factor_ref         0.1191
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16411
_reflns_number_total             20043
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic7b00277_si_002.cif
_cod_data_source_block           ba_ms9_sq
_cod_original_cell_volume        4894.75(15)
_cod_database_code               4345724
_audit_block_refno               2005
_audit_block_usercomment         'MS325, plate, yellow'
_chemical_oxdiff_formula         'C97 H92 N4 O12 P2 S4 Ta2'
_chemical_oxdiff_usercomment     'MS325, plate, yellow'
_shelx_estimated_absorpt_t_max   0.793
_shelx_estimated_absorpt_t_min   0.793
_reflns_odcompleteness_completeness 99.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_shelxl_version_number           2014/7
_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. Uiso/Uaniso restraints and constraints
C101 \\sim C102 \\sim C103 \\sim C104 \\sim C105 \\sim C106 \\sim C107: within
0.5A with sigma of 0.04 and sigma for terminal atoms of 0.04
C201 \\sim C202 \\sim C203 \\sim C204 \\sim C205 \\sim C206 \\sim C207: within
0.5A with sigma of 0.04 and sigma for terminal atoms of 0.04
3. Rigid body (RIGU) restrains
 C91, C92, C93, C94, C95, C96, C97
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C81, C82, C83, C84, C85, C86, C87
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C101, C102, C103, C104, C105, C106, C107
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C201, C202, C203, C204, C205, C206, C207
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C201)=Sof(C202)=Sof(H202)=Sof(C203)=Sof(H203)=Sof(C204)=Sof(H204)=
 Sof(C205)=Sof(H205)=Sof(C206)=Sof(H206)=Sof(C207)=Sof(H20A)=Sof(H20B)=
 Sof(H20C)=1-FVAR(1)
 Sof(C101)=Sof(C102)=Sof(H102)=Sof(C103)=Sof(H103)=Sof(C104)=Sof(H104)=
 Sof(C105)=Sof(H105)=Sof(C106)=Sof(H106)=Sof(C107)=Sof(H10A)=Sof(H10B)=
 Sof(H10C)=FVAR(1)
5.a Free rotating group:
 C91(C92,C93,C94,C95,C96,C97), C81(C82,C83,C84,C85,C86,C87), C101(C102,C103,
 C104,C105,C106,C107), C201(C202,C203,C204,C205,C206,C207)
5.b Ternary CH refined with riding coordinates:
 C7(H7), C43(H43)
5.c Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C58(H58A,H58B)
5.d Me refined with riding coordinates:
 C107(H10A,H10B,H10C), C207(H20A,H20B,H20C)
5.e Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C11(H11), C13(H13), C18(H18),
 C19(H19), C20(H20), C21(H21), C24(H24), C26(H26), C28(H28), C32(H32), C33(H33),
  C34(H34), C35(H35), C36(H36), C39(H39), C40(H40), C41(H41), C42(H42),
 C45(H45), C47(H47), C49(H49), C54(H54), C55(H55), C56(H56), C57(H57), C60(H60),
  C62(H62), C64(H64), C68(H68), C69(H69), C70(H70), C71(H71), C72(H72),
 C92(H92), C93(H93), C94(H94), C95(H95), C96(H96), C82(H82), C83(H83), C84(H84),
  C85(H85), C86(H86), C102(H102), C103(H103), C104(H104), C105(H105),
 C106(H106), C202(H202), C203(H203), C204(H204), C205(H205), C206(H206)
5.f Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C65(H65A,H65B,H65C), C66(H66A,
 H66B,H66C), C97(H97A,H97B,H97C), C87(H87A,H87B,H87C)
;
_shelx_res_checksum              16307
_shelx_hkl_checksum              74518
_shelx_fab_checksum              53962
_olex2_submission_special_instructions 'No special instructions were received'
_cell_oxdiff_length_a            13.8800(2)
_cell_oxdiff_length_b            19.0045(4)
_cell_oxdiff_length_c            20.1978(3)
_cell_oxdiff_angle_alpha         74.5788(15)
_cell_oxdiff_angle_beta          89.5752(13)
_cell_oxdiff_angle_gamma         72.9103(16)
_cell_oxdiff_volume              4894.74(14)
_cell_oxdiff_measurement_reflns_used 23569
_platon_squeeze_void_probe_radius 1.20