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_4345720
_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         'C39 H37 F3 N2 O3 P S Ta'
_chemical_formula_sum            'C39 H37 F3 N2 O3 P S Ta'
_chemical_formula_weight         882.68
_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_sb58
_audit_creation_date             2016-04-13
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.16 svn.r3265 for OlexSys, GUI svn.r5155)
;
_audit_update_record
'13.04.2016 14:15:20 CEST UTC+02:00  encif 1.43'
_cell_angle_alpha                82.1604(16)
_cell_angle_beta                 82.5253(15)
_cell_angle_gamma                89.5979(15)
_cell_formula_units_Z            4
_cell_length_a                   10.24496(17)
_cell_length_b                   18.6808(4)
_cell_length_c                   19.1934(4)
_cell_measurement_reflns_used    22332
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      70.5870
_cell_measurement_theta_min      4.3430
_cell_volume                     3607.84(12)
_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      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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    -72.00  26.00   1.00    3.00    --    0.00 -38.00  60.00   98
  2  \w    -70.00  30.00   1.00    3.00    --    0.00 -77.00 -30.00  100
  3  \w    -30.00  70.00   1.00    3.00    --    0.00  77.00  90.00  100
  4  \w    -37.00  12.00   1.00    3.00    --   10.00 108.00 -30.71   49
  5  \w    -35.00   9.00   1.00    3.00    --   14.00 112.00 128.45   44
  6  \w    -35.00  10.00   1.00    3.00    --   14.00 111.00-111.96   45
  7  \w    -21.00  11.00   1.00    3.00    --   26.00 109.00  24.04   32
  8  \w    -33.00  -3.00   1.00    3.00    --   26.00 127.00-152.77   30
  9  \w    -37.00 -11.00   1.00   10.00    --   30.00 141.00  78.24   26
 10  \w     -1.00  26.00   1.00   10.00    --   38.00  94.00  85.39   27
 11  \w      6.00  33.00   1.00   10.00    --   42.00  88.00 173.36   27
 12  \w      5.00  32.00   1.00   10.00    --   42.00  90.00 -69.91   27
 13  \w     12.00  38.00   1.00   10.00    --   46.00  84.00 -10.53   26
 14  \w     12.00  38.00   1.00   10.00    --   46.00  84.00-104.18   26
 15  \w     12.00  38.00   1.00   10.00    --   46.00  84.00  46.50   26
 16  \w     12.00  38.00   1.00   10.00    --   46.00  84.00 125.79   26
 17  \w     13.00  40.00   1.00   10.00    --   46.00  83.00-145.96   27
 18  \w     13.00  45.00   1.00   10.00    --   46.00  82.00 -31.33   32
 19  \w     18.00  46.00   1.00   10.00    --   50.00  80.00 176.54   28
 20  \w     18.00  46.00   1.00   10.00    --   50.00  80.00  74.28   28
 21  \w     18.00  46.00   1.00   10.00    --   50.00  81.00 117.74   28
 22  \w     19.00  49.00   1.00   10.00    --   50.00  78.00 -53.12   30
 23  \w     18.00  46.00   1.00   10.00    --   50.00  80.00-107.79   28
 24  \w     18.00  46.00   1.00   10.00    --   50.00  80.00 -68.21   28
 25  \w     17.00  45.00   1.00   10.00    --   50.00  82.00  -5.48   28
 26  \w     19.00  47.00   1.00   10.00    --   50.00  79.00-140.06   28
 27  \w     24.00 124.00   1.00   10.00    --   54.00  77.00-150.00  100
 28  \w     23.00 111.00   1.00   10.00    --   54.00-125.00  60.00   88
 29  \w    -15.00  75.00   1.00   10.00    --   54.00 -57.00  60.00   90
 30  \w     25.00 124.00   1.00   10.00    --   54.00  76.00 140.41   99
 31  \w     24.00 124.00   1.00   10.00    --   54.00  77.00 120.00  100
 32  \w    -15.00  75.00   1.00   10.00    --   54.00 -57.00 150.00   90
 33  \w     24.00 124.00   1.00   10.00    --   54.00  77.00-120.00  100
 34  \w      7.00  99.00   1.00   10.00    --   54.00-105.00 -37.00   92
 35  \w     24.00 124.00   1.00   10.00    --   54.00  77.00 -60.00  100
 36  \w     24.00  96.00   1.00   10.00    --   54.00  77.00-180.00   72
 37  \w     26.00  53.00   1.00   10.00    --   54.00  77.00  30.00   27
 38  \w     25.00  52.00   1.00   10.00    --   54.00  77.00 -90.00   27
 39  \w     29.00  55.00   1.00   10.00    --   58.00  77.00 160.71   26
 40  \w     31.00  56.00   1.00   10.00    --   58.00  74.00 -68.49   25
 41  \w     30.00  56.00   1.00   10.00    --   58.00  74.00 148.48   26
 42  \w     30.00  55.00   1.00   10.00    --   58.00  75.00 -99.46   25
 43  \w     30.00  57.00   1.00   10.00    --   58.00  74.00  83.73   27
 44  \w     31.00  56.00   1.00   10.00    --   58.00  74.00-173.67   25
 45  \w     87.00 114.00   1.00   10.00    --   58.00  75.00  60.06   27
 46  \w     29.00  56.00   1.00   10.00    --   58.00  75.00  60.06   27
 47  \w    103.00 128.00   1.00   10.00    --   58.00  75.00  11.81   25
 48  \w     29.00  56.00   1.00   10.00    --   58.00  75.00  11.81   27
 49  \w     98.00 124.00   1.00   10.00    --   58.00  74.00-173.67   26
 50  \w     28.00  54.00   1.00   10.00    --   58.00  77.00 -40.99   26
 51  \w     29.00  54.00   1.00   10.00    --   58.00  77.00  91.68   25
 52  \w     34.00  60.00   1.00   10.00    --   62.00  77.00 153.24   26
 53  \w     36.00  80.00   1.00   10.00    --   62.00  74.00 -94.57   44
 54  \w     37.00  63.00   1.00   10.00    --   62.00  72.00-176.34   26
 55  \w     40.00  65.00   1.00   10.00    --   62.00  64.00  21.83   25
 56  \w     45.00 130.00   1.00   10.00    --   62.00  57.00 132.67   85
 57  \w     32.00  57.00   1.00   10.00    --   62.00  77.00 -33.14   25
 58  \w     36.00  63.00   1.00   10.00    --   62.00  70.00  39.12   27
 59  \w     51.00  89.00   1.00   10.00    --   66.00  75.00 -24.89   38
 60  \w     41.00  68.00   1.00   10.00    --   66.00  71.00  63.80   27
 61  \w     40.00  67.00   1.00   10.00    --   66.00  74.00   9.21   27
 62  \w     38.00  65.00   1.00   10.00    --   66.00  75.00-176.84   27
 63  \w     38.00  64.00   1.00   10.00    --   66.00  76.00-121.31   26
 64  \w     38.00  64.00   1.00   10.00    --   66.00  74.00 -75.03   26
 65  \w     44.00  72.00   1.00   10.00    --   70.00  72.00-168.56   28
 66  \w     51.00 138.00   1.00   10.00    --   70.00  59.00 158.72   87
 67  \w     42.00  86.00   1.00   10.00    --   70.00  77.00-117.55   44
 68  \w     46.00  75.00   1.00   10.00    --   70.00  67.00 -48.82   29
 69  \w     41.00 123.00   1.00   10.00    --   70.00  76.00  72.44   82
 70  \w     47.00  73.00   1.00   10.00    --   70.00  71.00  53.96   26
 71  \w     49.00  76.00   1.00   10.00    --   74.00  72.00 -81.40   27
 72  \w     46.00  72.00   1.00   10.00    --   74.00  76.00-147.50   26
 73  \w    117.00 142.00   1.00   10.00    --   74.00  69.00 111.78   25
 74  \w     49.00  81.00   1.00   10.00    --   74.00  69.00 111.78   32
 75  \w     48.00  74.00   1.00   10.00    --   74.00  70.00 -89.63   26
 76  \w     45.00  74.00   1.00   10.00    --   74.00  76.00-162.55   29
 77  \w     47.00  78.00   1.00   10.00    --   74.00  72.00  24.54   31
 78  \w     53.00 113.00   1.00   10.00    --   78.00  70.00-129.38   60
 79  \w     48.00  74.00   1.00   10.00    --   78.00  77.00 166.42   26
 80  \w     48.00  74.00   1.00   10.00    --   78.00  77.00   8.24   26
 81  \w     56.00  90.00   1.00   10.00    --   78.00  65.00 -12.20   34
 82  \w     54.00  80.00   1.00   10.00    --   78.00  68.00 143.82   26
 83  \w     59.00  85.00   1.00   16.00    --   82.00  65.00  42.29   26
 84  \w     58.00  84.00   1.00   16.00    --   82.00  68.00 -99.32   26
 85  \w     60.00  93.00   1.00   16.00    --   82.00  51.00  52.03   33
 86  \w     56.00  93.00   1.00   16.00    --   86.00  77.00  66.87   37
 87  \w     58.00  84.00   1.00   16.00    --   86.00  74.00 137.41   26
 88  \w     64.00 110.00   1.00   16.00    --   86.00  49.00 -64.25   46
 89  \w     64.00 122.00   1.00   16.00    --   86.00  64.00   0.13   58
 90  \w     62.00 160.00   1.00   16.00    --   90.00  74.00  40.31   98
 91  \w     62.00  88.00   1.00   16.00    --   90.00  74.00 -63.70   26
 92  \w     68.00 119.00   1.00   16.00    --   90.00  46.00 -46.48   51
 93  \w     79.00 121.00   1.00   16.00    --   90.00  57.00-142.62   42
 94  \w     74.00 100.00   1.00   16.00    --   94.00  60.00-120.86   26
 95  \w     66.00  92.00   1.00   16.00    --   94.00  73.00-172.02   26
 96  \w     74.00 119.00   1.00   16.00    --  102.00  74.00 -74.98   45
 97  \w    143.00 169.00   1.00   16.00    --  102.00  73.00 118.90   26
 98  \w     74.00 102.00   1.00   16.00    --  102.00  73.00 118.90   28
 99  \w     76.00 102.00   1.00   16.00    --  102.00  72.00-103.13   26
100  \w    118.00 164.00   1.00   16.00    --  106.00  64.00  66.94   46
101  \w     84.00 114.00   1.00   16.00    --  106.00  64.00  66.94   30
102  \w     85.00 175.00   1.00   16.00    --  108.00  64.00-180.00   90
103  \w     83.00 177.00   1.00   16.00    --  108.00  38.00 120.00   94
104  \w     86.00 173.00   1.00   16.00    --  108.00  64.00  30.00   87
105  \w     85.00 112.00   1.00   16.00    --  108.00  64.00 -30.00   27
106  \w     85.00 116.00   1.00   16.00    --  108.00  64.00 150.00   31
107  \w     85.00 111.00   1.00   16.00    --  108.00  64.00-120.00   26
108  \w     86.00 113.00   1.00   16.00    --  108.00  64.00-150.00   27
109  \w     79.00 110.00   1.00   16.00    --  108.00  77.00 120.00   31
110  \w     78.00 175.00   1.00   16.00    --  108.00  77.00 -90.00   97
111  \w     78.00 104.00   1.00   16.00    --  108.00  77.00  60.00   26
112  \w     78.00 175.00   1.00   16.00    --  108.00  77.00 -60.00   97
113  \w     78.00 104.00   1.00   16.00    --  108.00  77.00   0.00   26
114  \w    114.00 175.00   1.00   16.00    --  108.00  77.00  90.00   61
115  \w     78.00 104.00   1.00   16.00    --  108.00  77.00  90.00   26
116  \w     87.00 113.00   1.00   16.00    --  108.00-111.00-180.00   26
117  \w    134.00 160.00   1.00   16.00    --  108.00  77.00 -30.00   26
118  \w     79.00 104.00   1.00   16.00    --  108.00  77.00 -30.00   25
119  \w     80.00 107.00   1.00   16.00    --  108.00  77.00-180.00   27
120  \w     79.00 168.00   1.00   16.00    --  108.00  77.00 150.00   89
121  \w    140.00 178.00   1.00   16.00    --  108.00  77.00-120.00   38
122  \w     78.00 104.00   1.00   16.00    --  108.00  77.00-120.00   26
123  \w     99.00 145.00   1.00   16.00    --  108.00 -92.00-120.00   46
124  \w     37.00  64.00   1.00   16.00    --  108.00 -92.00-120.00   27
125  \w     85.00 160.00   1.00   16.00    --  108.00  64.00  90.00   75
126  \w     79.00 172.00   1.00   16.00    --  108.00  77.00-150.00   93
127  \w     78.00 104.00   1.00   16.00    --  108.00  77.00  30.00   26
128  \w     85.00 166.00   1.00   16.00    --  108.00  64.00   0.00   81
129  \w     41.00 131.00   1.00   16.00    --  108.00 -64.00-120.00   90
130  \w     38.00 138.00   1.00   16.00    --  108.00 -77.00  60.00  100
131  \w     37.00 115.00   1.00   16.00    --  108.00-111.00  60.00   78
132  \w     36.00 115.00   1.00   16.00    --  108.00-111.00-120.00   79
133  \w     84.00 146.00   1.00   16.00    --  108.00  38.00  30.00   62
134  \w     84.00 160.00   1.00   16.00    --  108.00  38.00   0.00   76
135  \w     86.00 146.00   1.00   16.00    --  108.00  38.00 -90.00   60
136  \w     85.00 111.00   1.00   16.00    --  108.00  64.00  60.00   26
;
_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_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0200193000
_diffrn_orient_matrix_UB_12      -0.0279840000
_diffrn_orient_matrix_UB_13      0.0771313000
_diffrn_orient_matrix_UB_21      -0.1465785000
_diffrn_orient_matrix_UB_22      -0.0219333000
_diffrn_orient_matrix_UB_23      0.0167220000
_diffrn_orient_matrix_UB_31      0.0334350000
_diffrn_orient_matrix_UB_32      -0.0752759000
_diffrn_orient_matrix_UB_33      -0.0211959000
_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  0.0819
_diffrn_reflns_av_unetI/netI     0.0506
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            97353
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.832
_diffrn_reflns_theta_min         3.568
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.055
_exptl_absorpt_correction_T_max  0.616
_exptl_absorpt_correction_T_min  0.389
_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            'light yellow'
_exptl_crystal_density_diffrn    1.625
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1760
_exptl_crystal_size_max          0.210
_exptl_crystal_size_mid          0.103
_exptl_crystal_size_min          0.102
_refine_diff_density_max         1.069
_refine_diff_density_min         -1.109
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.003
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     905
_refine_ls_number_reflns         13730
_refine_ls_number_restraints     144
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0522
_refine_ls_R_factor_gt           0.0343
_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^)+(0.0398P)^2^+0.3843P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0731
_refine_ls_wR_factor_ref         0.0796
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10820
_reflns_number_total             13730
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic7b00277_si_002.cif
_cod_data_source_block           ba_sb58
_cod_original_cell_volume        3607.85(12)
_cod_database_code               4345720
_audit_block_refno               2700
_audit_block_usercomment         'sb496b, irregular, yellow'
_chemical_oxdiff_formula         'C39 H37 F3 N2 O3 P1 S1 Ta1'
_chemical_oxdiff_usercomment     'sb496b, irregular, yellow'
_shelx_estimated_absorpt_t_max   0.539
_shelx_estimated_absorpt_t_min   0.539
_reflns_odcompleteness_completeness 99.98
_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. Restrained distances
 C91-F1 \\sim C91-F2 \\sim C91-F3 \\sim C92-F51 \\sim C92-F52 \\sim C92-F53
 with sigma of 0.02
 F1-F2 \\sim F1-F3 \\sim F2-F3 \\sim F51-F52 \\sim F51-F53 \\sim F52-F53
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 O1, O2, O3, O51, O52, O53, S1, S51, C91, C92, F1, F2, F3, F51, F52, F53
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C14(H14A,H14B), C35(H35A,H35B), C37(H37A,H37B), C51(H51A,H51B),
 C64(H64A,H64B), C85(H85A,H85B), C87(H87A,H87B)
4.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),
 C54(H54), C55(H55), C56(H56), C57(H57), C59(H59), C60(H60), C61(H61), C62(H62),
  C63(H63), C67(H67), C68(H68), C69(H69), C70(H70), C72(H72), C73(H73),
 C74(H74), C75(H75), C76(H76), C78(H78), C79(H79), C80(H80), C81(H81), C82(H82)
4.c Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C38(H38A,H38B,H38C), C86(H86A,H86B,H86C), C88(H88A,H88B,
 H88C)
;
_shelx_res_checksum              97276
_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 2.311
_oxdiff_exptl_absorpt_empirical_full_min 0.508
_cell_oxdiff_length_a            10.24496(17)
_cell_oxdiff_length_b            18.6808(4)
_cell_oxdiff_length_c            19.1934(4)
_cell_oxdiff_angle_alpha         82.1604(16)
_cell_oxdiff_angle_beta          82.5253(15)
_cell_oxdiff_angle_gamma         89.5979(15)
_cell_oxdiff_volume              3607.84(12)
_cell_oxdiff_measurement_reflns_used 22332