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_4345723
_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
'C36 H34 I2 N2 P Ta, 0.33(C4 H10 O), 0.17(C7 H7)'
_chemical_formula_sum            'C38.5 H38.5 I2 N2 O0.33 P Ta'
_chemical_formula_weight         1000.26
_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_ms14
_audit_creation_date             2016-09-05
_audit_creation_method
;
Olex2 1.2
(compiled Aug 23 2016 16:59:57 for OlexSys, GUI svn.r5221)
;
_audit_update_record
'05.09.2016 16:47:34 CEST UTC+02:00  encif 1.46'
_cell_angle_alpha                76.866(11)
_cell_angle_beta                 86.362(18)
_cell_angle_gamma                71.547(12)
_cell_formula_units_Z            6
_cell_length_a                   12.964(7)
_cell_length_b                   16.745(9)
_cell_length_c                   29.705(15)
_cell_measurement_reflns_used    8162
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.52
_cell_measurement_theta_min      2.41
_cell_volume                     5957(5)
_computing_cell_refinement
;
SAINT (see _computing_data_reduction). Includes estimated systematic errors
 of the unit cell constants from Monte Carlo simulations.
;
_computing_data_collection       'SMART-5.631 (Bruker AXS, 2003)'
_computing_data_reduction
'SAINT (Bruker AXS, 1997-2013),SADABS-2012_1 (Sheldrick and Bruker AXS, 1997-2014)'
_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 polyether oil / N~2~'
_diffrn_ambient_temperature      100(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.19
_diffrn_detector_type            CCD-PXL-KAF2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker AXS Smart 1000'
_diffrn_measurement_method       '\f- and \w-scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0722
_diffrn_reflns_av_unetI/netI     0.0661
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            122425
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.544
_diffrn_reflns_theta_min         1.656
_diffrn_source                   'sealed X-Ray tube (Mo)'
_diffrn_source_type              'fine focus tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.391
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6739
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
multi-scan from symmetry-related measurements (Blessing 1995)
SADABS (see _computing_data_reduction)
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.673
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2881
_exptl_crystal_size_max          0.160
_exptl_crystal_size_mid          0.140
_exptl_crystal_size_min          0.110
_refine_diff_density_max         4.006
_refine_diff_density_min         -2.124
_refine_diff_density_rms         0.189
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1231
_refine_ls_number_reflns         27365
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0813
_refine_ls_R_factor_gt           0.0490
_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^)+(0.0486P)^2^+27.7704P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1052
_refine_ls_wR_factor_ref         0.1184
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19394
_reflns_number_total             27365
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic7b00277_si_002.cif
_cod_data_source_block           ba_ms14_sq
_cod_original_cell_volume        5956(5)
_cod_original_formula_sum        'C38.50 H38.50 I2 N2 O0.33 P Ta'
_cod_database_code               4345723
_audit_block_refno               2068
_shelx_estimated_absorpt_t_max   0.644
_shelx_estimated_absorpt_t_min   0.540
_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. Others
 Fixed Sof: C304(0.5) H30D(0.5) H30E(0.5) H30F(0.5)
3.a Ternary CH refined with riding coordinates:
 C1(H1), C81(H81), C41(H41)
3.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C96(H96A,H96B), C56(H56A,H56B), C201(H20A,H20B), C203(H20F,
 H20G)
3.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C11(H11), C13(H13), C19(H19),
 C20(H20), C21(H21), C22(H22), C24(H24), C26(H26), C28(H28), C32(H32), C33(H33),
  C34(H34), C35(H35), C36(H36), C84(H84), C85(H85), C86(H86), C87(H87),
 C89(H89), C91(H91), C93(H93), C99(H99), C100(H100), C101(H101), C102(H102),
 C104(H104), C106(H106), C108(H108), C112(H112), C113(H113), C114(H114),
 C115(H115), C116(H116), C44(H44), C45(H45), C46(H46), C47(H47), C49(H49),
 C51(H51), C53(H53), C59(H59), C60(H60), C61(H61), C62(H62), C64(H64), C66(H66),
  C68(H68), C72(H72), C73(H73), C74(H74), C75(H75), C76(H76), C302(H302),
 C303(H303)
3.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C94(H94A,H94B,H94C), C95(H95A,H95B,H95C), C109(H10A,H10B,H10C),
 C110(H11A,H11B,H11C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C69(H69A,H69B,
 H69C), C70(H70A,H70B,H70C), C202(H20C,H20D,H20E), C204(H20H,H20I,H20J),
 C304(H30D,H30E,H30F)
;
_shelx_res_checksum              1259
_shelx_hkl_checksum              46505
_shelx_fab_checksum              31845
_olex2_submission_special_instructions 'No special instructions were received'
_platon_squeeze_void_probe_radius 1.20