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_4345718
_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_absolute_configuration ad
_chemical_formula_moiety
'0.5(C44 H53 Li2 N2 O2 P), 0.5(C44 H52 Li2 N2 O2 P), 0.5(C4 H9 O)'
_chemical_formula_sum            'C46 H57 Li2 N2 O2.5 P'
_chemical_formula_weight         722.78
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      4
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ba_ms36
_audit_creation_date             2016-06-30
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.16 svn.r3265 for OlexSys, GUI svn.r5155)
;
_audit_update_record
'30.06.2016 15:54:28 CEST UTC+02:00  encif 1.46'
_cell_angle_alpha                90
_cell_angle_beta                 97.4873(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.0189(2)
_cell_length_b                   23.7073(4)
_cell_length_c                   15.0077(3)
_cell_measurement_reflns_used    17841
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      28.0100
_cell_measurement_theta_min      3.5170
_cell_volume                     4239.77(13)
_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 0.998
_diffrn_measured_fraction_theta_max 0.995
_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    -27.00   1.00   0.50   15.00    --    4.00  79.00 -70.95   56
  2  \w     59.00  95.00   0.50   15.00    --   26.87  57.00  30.00   72
  3  \w     -2.00  23.00   0.50   15.00    --   26.87  77.00 150.00   50
  4  \w     13.00  96.00   0.50   15.00    --   26.87  77.00  60.00  166
  5  \w    -32.00  27.00   0.50   15.00    --   26.87 -80.00 -65.77  118
  6  \w     34.00  59.00   0.50   15.00    --   26.87 -80.00 -65.77   50
  7  \w    -42.00   5.00   0.50   15.00    --   26.87 -77.00  60.00   94
  8  \w     30.00  57.00   0.50   15.00    --   26.87 -77.00  60.00   54
  9  \w     -4.00  24.00   0.50   15.00    --   26.87  80.00  16.48   56
 10  \w    -44.00  59.00   0.50   15.00    --   26.87 -80.00  -9.05  206
 11  \w      5.00  61.00   0.50   15.00    --   26.87  38.00-180.00  112
 12  \w     14.00  76.00   0.50   15.00    --   26.87  57.00 -90.00  124
 13  \w      6.00  37.00   0.50   15.00    --   26.87  57.00  60.00   62
 14  \w     16.00  96.00   0.50   15.00    --   26.87  57.00 -30.00  160
 15  \w      2.00  87.00   0.50   15.00    --   26.87  77.00-180.00  170
 16  \w     -3.00  25.00   0.50   15.00    --   26.87  79.00 -78.44   56
 17  \w    -39.00 -12.00   0.50   15.00    --   28.00 -79.00  30.49   54
 18  \w    -43.00  60.00   0.50   15.00    --   28.00 -80.00 114.26  206
 19  \w     23.00  59.00   0.50   15.00    --   28.00 -78.00-101.04   72
 20  \w    -42.00  -5.00   0.50   15.00    --   28.00 -78.00-101.04   74
 21  \w     22.00  59.00   0.50   15.00    --   28.00 -79.00  30.49   74
 22  \w    -39.00  60.00   0.50   15.00    --   28.00 -80.00-166.16  198
;
_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      -0.0053809000
_diffrn_orient_matrix_UB_12      -0.0259111000
_diffrn_orient_matrix_UB_13      -0.0237617000
_diffrn_orient_matrix_UB_21      0.0264273000
_diffrn_orient_matrix_UB_22      -0.0142662000
_diffrn_orient_matrix_UB_23      0.0386481000
_diffrn_orient_matrix_UB_31      -0.0530494000
_diffrn_orient_matrix_UB_32      -0.0045159000
_diffrn_orient_matrix_UB_33      0.0146605000
_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  0.0722
_diffrn_reflns_av_unetI/netI     0.0624
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            99467
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.337
_diffrn_reflns_theta_min         3.233
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.104
_exptl_absorpt_correction_T_max  0.98449
_exptl_absorpt_correction_T_min  0.98449
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.132
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1552
_exptl_crystal_size_max          0.242
_exptl_crystal_size_mid          0.217
_exptl_crystal_size_min          0.149
_refine_diff_density_max         0.772
_refine_diff_density_min         -0.319
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 6552 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(4)
_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     978
_refine_ls_number_reflns         21025
_refine_ls_number_restraints     64
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0778
_refine_ls_R_factor_gt           0.0580
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0547P)^2^+2.2970P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1277
_refine_ls_wR_factor_ref         0.1384
_reflns_Friedel_coverage         0.953
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                17022
_reflns_number_total             21025
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic7b00277_si_002.cif
_cod_data_source_block           ba_ms36
_cod_original_cell_volume        4239.76(12)
_cod_original_sg_symbol_H-M      'P 21'
_cod_original_formula_sum        'C46 H57 Li2 N2 O2.50 P'
_cod_database_code               4345718
_audit_block_refno               2478
_audit_block_usercomment         'Li2NPN irregular colourless'
_chemical_oxdiff_formula         'C46 H57 Li2 N2 O2.5 P1'
_chemical_oxdiff_usercomment     'Li2NPN irregular colourless'
_shelx_estimated_absorpt_t_max   0.990
_shelx_estimated_absorpt_t_min   0.990
_reflns_odcompleteness_completeness 99.75
_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. Rigid body (RIGU) restrains
 O101, C101, C102, C103, C104
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O52, C91, C92, C93, C94
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O2, C41, C42, C43, C44
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C14(H14A,H14B), C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B),
 C40(H40A,H40B), C41(H41A,H41B), C43(H43A,H43B), C57(H57A,H57B), C64(H64A,H64B),
  C87(H87A,H87B), C88(H88A,H88B), C89(H89A,H89B), C90(H90A,H90B), C91(H91A,
 H91B), C103(H10D,H10E)
3.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C10(H10), C11(H11), C12(H12), C13(H13),
 C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C22(H22), C24(H24), C26(H26),
  C30(H30), C32(H32), C34(H34), C52(H52), C53(H53), C54(H54), C55(H55),
 C60(H60), C61(H61), C62(H62), C63(H63), C66(H66), C67(H67), C68(H68), C69(H69),
  C70(H70), C72(H72), C74(H74), C76(H76), C80(H80), C82(H82), C84(H84),
 C93(H93), C101(H101)
3.c Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C35(H35A,H35B,H35C), C36(H36A,H36B,
 H36C), C42(H42A,H42B,H42C), C44(H44A,H44B,H44C), C77(H77A,H77B,H77C), C78(H78A,
 H78B,H78C), C85(H85A,H85B,H85C), C86(H86A,H86B,H86C), C92(H92A,H92B,H92C),
 C94(H94A,H94B,H94C), C102(H10A,H10B,H10C), C104(H10F,H10G,H10H)
;
_shelx_res_checksum              83720
_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 1.182
_oxdiff_exptl_absorpt_empirical_full_min 0.897
_cell_oxdiff_length_a            12.0223(3)
_cell_oxdiff_length_b            23.7054(7)
_cell_oxdiff_length_c            15.0060(4)
_cell_oxdiff_angle_alpha         89.915(2)
_cell_oxdiff_angle_beta          97.523(2)
_cell_oxdiff_angle_gamma         90.074(2)
_cell_oxdiff_volume              4239.8(2)
_cell_oxdiff_measurement_reflns_used 17841