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_4345721
_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         'C42 H48 N2 P Si Ta'
_chemical_formula_sum            'C44.5 H54 N2 P Si Ta'
_chemical_formula_weight         856.90
_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     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ba_sb62
_audit_creation_date             2016-05-19
_audit_creation_method
;
Olex2 1.2
(compiled Aug 23 2016 16:59:57 for OlexSys, GUI svn.r5221)
;
_audit_update_record
'05.09.2016 16:43:06 CEST UTC+02:00  encif 1.46'
_cell_angle_alpha                90.3798(9)
_cell_angle_beta                 101.0855(10)
_cell_angle_gamma                104.7680(10)
_cell_formula_units_Z            2
_cell_length_a                   11.57180(14)
_cell_length_b                   12.44923(14)
_cell_length_c                   14.67713(17)
_cell_measurement_reflns_used    51261
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      70.6210
_cell_measurement_theta_min      3.6740
_cell_volume                     2002.94(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.991
_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    -12.00  37.00   1.00    1.00    --    0.00 -89.00  24.00   49
  2  \w    -21.00  69.00   1.00    1.00    --    0.00  57.00  90.00   90
  3  \w    -72.00  26.00   1.00    1.00    --    0.00 -38.00 120.00   98
  4  \w    -21.00  69.00   1.00    1.00    --    0.00  57.00-150.00   90
  5  \w    -21.00  69.00   1.00    1.00    --    0.00  57.00 -90.00   90
  6  \w    -36.00   8.00   1.00    1.00    --   14.00 113.00 -56.56   44
  7  \w    -40.00 -13.00   1.00    4.00    --   30.00 145.00 151.27   27
  8  \w      2.00  33.00   1.00    4.00    --   38.00  88.00 -10.29   31
  9  \w      5.00  32.00   1.00    4.00    --   42.00  90.00  33.03   27
 10  \w      6.00  33.00   1.00    4.00    --   42.00  88.00 150.87   27
 11  \w      6.00  33.00   1.00    4.00    --   42.00  88.00  60.83   27
 12  \w      8.00  38.00   1.00    4.00    --   42.00  84.00 -55.24   30
 13  \w     14.00  46.00   1.00    4.00    --   46.00  81.00  96.44   32
 14  \w     13.00  40.00   1.00    4.00    --   46.00  83.00-157.19   27
 15  \w     14.00  46.00   1.00    4.00    --   46.00  81.00 -87.99   32
 16  \w     21.00 120.00   1.00    4.00    --   50.00  75.00-106.02   99
 17  \w     21.00 120.00   1.00    4.00    --   50.00  75.00  61.49   99
 18  \w     18.00  46.00   1.00    4.00    --   50.00  80.00 -12.62   28
 19  \w     18.00  46.00   1.00    4.00    --   50.00  80.00 154.55   28
 20  \w     20.00 120.00   1.00    4.00    --   50.00  77.00 -78.66  100
 21  \w     18.00  46.00   1.00    4.00    --   50.00  80.00 126.41   28
 22  \w     24.00 124.00   1.00    4.00    --   54.00  77.00 -30.00  100
 23  \w     25.00 124.00   1.00    4.00    --   54.00  75.00-159.53   99
 24  \w     24.00 124.00   1.00    4.00    --   54.00  77.00  30.00  100
 25  \w     24.00 124.00   1.00    4.00    --   54.00  77.00  90.00  100
 26  \w     24.00 124.00   1.00    4.00    --   54.00  77.00-120.00  100
 27  \w      1.00  96.00   1.00    4.00    --   54.00 -99.00-180.00   95
 28  \w    -16.00  84.00   1.00    4.00    --   54.00 -77.00  30.00  100
 29  \w     24.00 124.00   1.00    4.00    --   54.00  77.00 150.00  100
 30  \w     33.00 123.00   1.00    4.00    --   54.00  57.00-180.00   90
 31  \w     24.00 124.00   1.00    4.00    --   54.00  77.00 -90.00  100
 32  \w    -15.00  75.00   1.00    4.00    --   54.00 -57.00 -90.00   90
 33  \w     24.00 124.00   1.00    4.00    --   54.00  77.00 -60.00  100
 34  \w     23.00 111.00   1.00    4.00    --   54.00-125.00-180.00   88
 35  \w     29.00 128.00   1.00    4.00    --   58.00  76.00 178.40   99
 36  \w     30.00 128.00   1.00    4.00    --   58.00  74.00 129.44   98
 37  \w     30.00 127.00   1.00    4.00    --   58.00  73.00  67.42   97
 38  \w     29.00 128.00   1.00    4.00    --   58.00  75.00 -71.62   99
 39  \w     28.00 128.00   1.00    4.00    --   58.00  77.00   2.47  100
 40  \w     35.00 131.00   1.00    4.00    --   62.00  72.00  31.31   96
 41  \w     39.00 130.00   1.00    4.00    --   62.00  66.00 138.04   91
 42  \w     34.00 131.00   1.00    4.00    --   62.00  73.00-102.72   97
 43  \w     38.00 135.00   1.00    4.00    --   66.00  73.00-114.70   97
 44  \w     40.00 135.00   1.00    4.00    --   66.00  70.00  93.43   95
 45  \w     39.00 135.00   1.00    4.00    --   66.00  72.00 177.96   96
 46  \w     46.00 134.00   1.00    4.00    --   66.00  59.00  15.35   88
 47  \w     36.00 136.00   1.00    4.00    --   66.00  77.00 -64.37  100
 48  \w     41.00 140.00   1.00    4.00    --   70.00  76.00 123.96   99
 49  \w     42.00 140.00   1.00    4.00    --   70.00  74.00  93.33   98
 50  \w     48.00 140.00   1.00    4.00    --   70.00  51.00 -29.80   92
 51  \w     47.00 138.00   1.00    4.00    --   70.00  65.00-103.15   91
 52  \w     49.00 139.00   1.00    4.00    --   70.00  57.00-164.05   90
 53  \w     49.00 139.00   1.00    4.00    --   70.00  57.00  74.91   90
 54  \w     51.00 145.00   1.00    4.00    --   74.00  46.00   6.51   94
 55  \w     47.00 143.00   1.00    4.00    --   74.00  71.00-165.87   96
 56  \w     46.00 143.00   1.00    4.00    --   74.00  73.00-142.46   97
 57  \w     49.00 148.00   1.00    4.00    --   78.00  75.00 -58.50   99
 58  \w     49.00 148.00   1.00    4.00    --   78.00  76.00  27.24   99
 59  \w     49.00 148.00   1.00    4.00    --   78.00  75.00 -94.68   99
 60  \w     51.00 147.00   1.00    4.00    --   78.00  72.00  -1.07   96
 61  \w     61.00 152.00   1.00    8.00    --   82.00  53.00  87.83   91
 62  \w     61.00 151.00   1.00    8.00    --   82.00  57.00  90.01   90
 63  \w     53.00 152.00   1.00    8.00    --   82.00  76.00  88.45   99
 64  \w     60.00 155.00   1.00    8.00    --   86.00  70.00 -90.20   95
 65  \w     58.00 155.00   1.00    8.00    --   86.00  73.00-154.72   97
 66  \w     57.00 156.00   1.00    8.00    --   86.00  76.00-125.15   99
 67  \w     61.00 160.00   1.00    8.00    --   90.00  76.00-165.81   99
 68  \w     69.00 160.00   1.00    8.00    --   90.00  53.00  63.26   91
 69  \w     67.00 161.00   1.00    8.00    --   90.00  45.00 150.02   94
 70  \w     72.00 164.00   1.00    8.00    --   94.00  50.00 -35.80   92
 71  \w     71.00 167.00   1.00    8.00    --   98.00  71.00 166.81   96
 72  \w     85.00 175.00   1.00    8.00    --  108.00  64.00  30.00   90
 73  \w     38.00 130.00   1.00    8.00    --  108.00 -50.00 -30.00   92
 74  \w     85.00 175.00   1.00    8.00    --  108.00  64.00-120.00   90
 75  \w     78.00 178.00   1.00    8.00    --  108.00  77.00 120.00  100
 76  \w     85.00 175.00   1.00    8.00    --  108.00  64.00   0.00   90
 77  \w    100.00 178.00   1.00    8.00    --  108.00 111.00 -90.00   78
 78  \w     82.00 178.00   1.00    8.00    --  108.00  38.00  60.00   96
 79  \w     38.00 130.00   1.00    8.00    --  108.00 -50.00-180.00   92
 80  \w     85.00 175.00   1.00    8.00    --  108.00  64.00-150.00   90
 81  \w     36.00 146.00   1.00    8.00    --  108.00 -92.00 -30.00  110
 82  \w     82.00 178.00   1.00    8.00    --  108.00  38.00  30.00   96
 83  \w     36.00 116.00   1.00    8.00    --  108.00-111.00-150.00   80
 84  \w     85.00 175.00   1.00    8.00    --  108.00  64.00  60.00   90
 85  \w     85.00 175.00   1.00    8.00    --  108.00  64.00 150.00   90
 86  \w     85.00 175.00   1.00    8.00    --  108.00  64.00 -90.00   90
 87  \w     85.00 175.00   1.00    8.00    --  108.00  64.00 120.00   90
 88  \w     85.00 175.00   1.00    8.00    --  108.00  64.00  90.00   90
 89  \w     78.00 178.00   1.00    8.00    --  108.00  77.00 150.00  100
 90  \w    100.00 178.00   1.00    8.00    --  108.00 111.00   0.00   78
 91  \w     78.00 178.00   1.00    8.00    --  108.00  77.00  30.00  100
 92  \w     78.00 178.00   1.00    8.00    --  108.00  77.00-120.00  100
 93  \w     78.00 178.00   1.00    8.00    --  108.00  77.00-180.00  100
 94  \w     78.00 178.00   1.00    8.00    --  108.00  77.00   0.00  100
 95  \w     78.00 178.00   1.00    8.00    --  108.00  77.00 -30.00  100
 96  \w     78.00 178.00   1.00    8.00    --  108.00  77.00  90.00  100
 97  \w     78.00 178.00   1.00    8.00    --  108.00  77.00  60.00  100
 98  \w     78.00 178.00   1.00    8.00    --  108.00  77.00-150.00  100
 99  \w     78.00 178.00   1.00    8.00    --  108.00  77.00 -60.00  100
100  \w     82.00 178.00   1.00    8.00    --  108.00  38.00-180.00   96
101  \w     36.00 116.00   1.00    8.00    --  108.00-111.00 150.00   80
102  \w     36.00 116.00   1.00    8.00    --  108.00-111.00 -60.00   80
103  \w     78.00 178.00   1.00    8.00    --  108.00  77.00 -90.00  100
104  \w     85.00 175.00   1.00    8.00    --  108.00  64.00 -30.00   90
105  \f    120.00 240.00   1.00    1.00   0.00   0.00  40.00    --   120
106  \f    120.00 240.00   1.00    1.00   0.00   0.00 -40.00    --   120
107  \f      0.00 120.00   1.00    1.00   0.00   0.00  40.00    --   120
108  \f      0.00 120.00   1.00    1.00   0.00   0.00 -60.00    --   120
109  \f    120.00 240.00   1.00    1.00   0.00   0.00 -60.00    --   120
110  \f      0.00 120.00   1.00    1.00   0.00   0.00  60.00    --   120
111  \f      0.00 120.00   1.00    1.00   0.00   0.00 -40.00    --   120
112  \f    120.00 240.00   1.00    4.00  54.00  54.00 -60.00    --   120
113  \f    120.00 240.00   1.00    4.00  54.00  54.00  40.00    --   120
114  \f    120.00 240.00   1.00    4.00  54.00  54.00 -40.00    --   120
115  \f      0.00 120.00   1.00    4.00  54.00  54.00  60.00    --   120
116  \w    -12.00  91.00   1.00    4.00    --   54.00 -89.00  24.00  103
117  \f      0.00 120.00   1.00    4.00  54.00  54.00 -60.00    --   120
118  \f    120.00 240.00   1.00    4.00  54.00  54.00  60.00    --   120
119  \f    240.00 360.00   1.00    4.00  54.00  54.00 -60.00    --   120
120  \f      0.00 120.00   1.00    4.00  54.00  54.00  40.00    --   120
121  \f    240.00 360.00   1.00    4.00  54.00  54.00  40.00    --   120
122  \f    240.00 360.00   1.00    4.00  54.00  54.00  60.00    --   120
123  \f    240.00 360.00   1.00    4.00  54.00  54.00 -40.00    --   120
124  \w    -12.00  91.00   1.00    4.00    --   54.00 -89.00  24.00  103
125  \w    -12.00  42.00   1.00    4.00    --   54.00 -89.00  24.00   54
126  \f      0.00 120.00   1.00    4.00  54.00  54.00 -40.00    --   120
;
_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      -0.1366155000
_diffrn_orient_matrix_UB_12      -0.0601978000
_diffrn_orient_matrix_UB_13      -0.0136055000
_diffrn_orient_matrix_UB_21      0.0034522000
_diffrn_orient_matrix_UB_22      -0.0483976000
_diffrn_orient_matrix_UB_23      -0.0960183000
_diffrn_orient_matrix_UB_31      0.0327786000
_diffrn_orient_matrix_UB_32      -0.1023133000
_diffrn_orient_matrix_UB_33      0.0455533000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0402
_diffrn_reflns_av_unetI/netI     0.0182
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            94978
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.687
_diffrn_reflns_theta_min         3.678
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.964
_exptl_absorpt_correction_T_max  0.914
_exptl_absorpt_correction_T_min  0.635
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.421
_exptl_crystal_description       irregular
_exptl_crystal_F_000             874
_exptl_crystal_size_max          0.100
_exptl_crystal_size_mid          0.091
_exptl_crystal_size_min          0.016
_refine_diff_density_max         1.804
_refine_diff_density_min         -1.131
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     429
_refine_ls_number_reflns         7621
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0258
_refine_ls_R_factor_gt           0.0234
_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^)+(0.0370P)^2^+1.4355P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0589
_refine_ls_wR_factor_ref         0.0601
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7177
_reflns_number_total             7621
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic7b00277_si_002.cif
_cod_data_source_block           ba_sb62_sq
_cod_original_formula_sum        'C44.50 H54 N2 P Si Ta'
_cod_database_code               4345721
_audit_block_refno               2719
_audit_block_usercomment         'sb521, yellow, irregular'
_chemical_oxdiff_formula         'C44.5 H54 N2 P Si Ta'
_chemical_oxdiff_usercomment     'sb521, yellow, irregular'
_shelx_estimated_absorpt_t_max   0.587
_shelx_estimated_absorpt_t_min   0.587
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C1(H1A,H1B), C14(H14A,H14B), C35(H35A,H35B), C37(H37A,H37B), C39(H39A,H39B)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C17(H17), C18(H18), C19(H19), C20(H20), C22(H22), C23(H23), C24(H24),
  C25(H25), C26(H26), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32)
2.c Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C38(H38A,H38B,H38C), C40(H40A,H40B,H40C), C41(H41A,H41B,
 H41C), C42(H42A,H42B,H42C)
;
_shelx_res_checksum              50903
_shelx_hkl_checksum              98510
_shelx_fab_checksum              64387
_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 1.562
_oxdiff_exptl_absorpt_empirical_full_min 0.700
_cell_oxdiff_length_a            11.57180(14)
_cell_oxdiff_length_b            12.44923(14)
_cell_oxdiff_length_c            14.67713(17)
_cell_oxdiff_angle_alpha         90.3798(9)
_cell_oxdiff_angle_beta          101.0855(10)
_cell_oxdiff_angle_gamma         104.7680(10)
_cell_oxdiff_volume              2002.94(4)
_cell_oxdiff_measurement_reflns_used 51261
_platon_squeeze_void_probe_radius 1.20