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_4345727
_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         'C46 H60 N2 P3 Si Ta, C6 D6'
_chemical_formula_sum            'C52 H60 D6 N2 P3 Si Ta'
_chemical_formula_weight         1027.05
_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   mixed
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ba_jb24
_audit_creation_date             2016-02-24
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.16 svn.r3265 for OlexSys, GUI svn.r5155)
;
_audit_update_record
'24.02.2016 16:46:27 CET UTC+01:00  encif 1.38'
_cell_angle_alpha                96.7192(8)
_cell_angle_beta                 103.3852(9)
_cell_angle_gamma                110.8123(9)
_cell_formula_units_Z            2
_cell_length_a                   11.08257(12)
_cell_length_b                   11.90731(11)
_cell_length_c                   20.8619(2)
_cell_measurement_reflns_used    54004
_cell_measurement_temperature    100(1)
_cell_measurement_theta_max      32.3090
_cell_measurement_theta_min      3.3140
_cell_volume                     2442.63(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41p (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41p (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41p (Rigaku OD, 2015)'
_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    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_environment      perfluoro
_diffrn_ambient_temperature      100(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 0.998
_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    -25.00  15.00   0.50   20.00    --  -25.00 -95.00  -2.50   80
  2  \w      1.00  99.00   0.50   20.00    --   26.87  38.00 150.00  196
  3  \w    -20.00  69.00   0.50   20.00    --   26.87 -99.00-150.00  178
  4  \w      6.00  96.00   0.50   20.00    --   26.87  57.00-150.00  180
  5  \w    -20.00  69.00   0.50   20.00    --   26.87 -99.00   0.00  178
  6  \w      6.00  96.00   0.50   20.00    --   26.87  57.00  30.00  180
  7  \w      6.00  96.00   0.50   20.00    --   26.87  57.00 -60.00  180
  8  \w    -42.00  48.00   0.50   20.00    --   26.87 -57.00-120.00  180
  9  \w     -3.00  97.00   0.50   20.00    --   26.87  76.00 129.00  200
 10  \w    -42.00  48.00   0.50   20.00    --   26.87 -57.00 150.00  180
 11  \w    -42.00  48.00   0.50   20.00    --   26.87 -57.00  60.00  180
 12  \w     -3.00  97.00   0.50   20.00    --   26.87  77.00-120.00  200
 13  \w    -42.00  48.00   0.50   20.00    --   26.87 -57.00 -30.00  180
 14  \w     -3.00  97.00   0.50   20.00    --   26.87  77.00  30.00  200
 15  \w      6.00  96.00   0.50   20.00    --   26.87  57.00 -30.00  180
 16  \w      1.00  99.00   0.50   20.00    --   26.87  38.00 -60.00  196
 17  \w      6.00  89.00   0.50   20.00    --   26.87-132.00-175.65  166
 18  \f      0.00  76.00   0.50   20.00  26.87  26.87  40.00    --   152
 19  \f      0.00  68.00   0.50   20.00  26.87  26.87 -40.00    --   136
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0554275000
_diffrn_orient_matrix_UB_12      -0.0240709000
_diffrn_orient_matrix_UB_13      0.0129922000
_diffrn_orient_matrix_UB_21      0.0067937000
_diffrn_orient_matrix_UB_22      0.0606709000
_diffrn_orient_matrix_UB_23      0.0124028000
_diffrn_orient_matrix_UB_31      -0.0448742000
_diffrn_orient_matrix_UB_32      -0.0023515000
_diffrn_orient_matrix_UB_33      -0.0309905000
_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  0.0271
_diffrn_reflns_av_unetI/netI     0.0145
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_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       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            65308
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.123
_diffrn_reflns_theta_max         25.123
_diffrn_reflns_theta_min         3.073
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.409
_exptl_absorpt_correction_T_max  0.820
_exptl_absorpt_correction_T_min  0.776
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41p (Rigaku Oxford Diffraction, 2015)
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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.388
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1048
_exptl_crystal_size_max          0.156
_exptl_crystal_size_mid          0.128
_exptl_crystal_size_min          0.106
_refine_diff_density_max         1.008
_refine_diff_density_min         -2.067
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.477
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     549
_refine_ls_number_reflns         8717
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.477
_refine_ls_R_factor_all          0.0291
_refine_ls_R_factor_gt           0.0289
_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^)+7.9409P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0699
_refine_ls_wR_factor_ref         0.0699
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8682
_reflns_number_total             8717
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic7b00277_si_002.cif
_cod_data_source_block           ba_jb24
_cod_database_code               4345727
_audit_block_refno               2661
_audit_block_usercomment         'jb290, irregular, red'
_chemical_oxdiff_formula         'C52 H66 N2 P3 Si Ta'
_chemical_oxdiff_usercomment     'jb290, irregular, red'
_shelx_estimated_absorpt_t_max   0.795
_shelx_estimated_absorpt_t_min   0.795
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.07
_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.a Secondary CH2 refined with riding coordinates:
 C37(H37A,H37B), C38(H38A,H38B), C43(H43A,H43B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C9(H9), C11(H11), C13(H13), C17(H17),
 C18(H18), C19(H19), C20(H20), C24(H24), C26(H26), C28(H28), C32(H32), C33(H33),
  C34(H34), C35(H35), C36(H36), C51(D51), C52(D52), C53(D53), C54(D54),
 C55(D55), C56(D56)
2.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,
 H42B,H42C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C)
;
_shelx_res_checksum              81072
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.075
_oxdiff_exptl_absorpt_empirical_full_min 0.932
_cell_oxdiff_length_a            11.08257(12)
_cell_oxdiff_length_b            11.90731(11)
_cell_oxdiff_length_c            20.8619(2)
_cell_oxdiff_angle_alpha         96.7192(8)
_cell_oxdiff_angle_beta          103.3852(9)
_cell_oxdiff_angle_gamma         110.8123(9)
_cell_oxdiff_volume              2442.64(4)
_cell_oxdiff_measurement_reflns_used 54004