Synthesis and Reactivity of Group 4 Metal Benzyl Complexes Supported by Carbazolide-Based PNP Pincer Ligands.
Plundrich, Gudrun T.; Wadepohl, Hubert; Gade, Lutz H.; Inorganic chemistry 55 (2015) 353–; doi:10.1021/acs.inorgchem.5b02498

data_4344793
_publ_section_title
;
 Synthesis and Reactivity of Group 4 Metal Benzyl Complexes Supported by
 Carbazolide-Based PNP Pincer Ligands.
;
_journal_issue                   1
_journal_name_full               'Inorganic chemistry'
_journal_page_first              353
_journal_paper_doi               10.1021/acs.inorgchem.5b02498
_journal_volume                  55
_journal_year                    2015
_chemical_formula_moiety         'C46 H46 Cl3 Hf N P2'
_chemical_formula_sum            'C46 H46 Cl3 Hf N P2'
_chemical_formula_weight         959.62
_chemical_properties_physical    air-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                ga_gp22
_audit_creation_date
;
'Tue May 13 11:06:02 2014'
;
_audit_update_record             'Tue May 13 15:42:49 CEST 2014'
_cell_angle_alpha                76.9320(7)
_cell_angle_beta                 77.1622(7)
_cell_angle_gamma                71.0505(8)
_cell_formula_units_Z            2
_cell_length_a                   11.09282(10)
_cell_length_b                   11.09294(9)
_cell_length_c                   18.53238(15)
_cell_measurement_reflns_used    96106
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      33.7920
_cell_measurement_theta_min      3.6590
_cell_volume                     2073.43(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material
'encif (Wadepohl, 2009-14); encifer 1.4 (CCDC, 2011)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_environment      N~2~
_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 0.958
_diffrn_measurement_details
;
  1 omega  -38.00   52.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481  -57.0000  120.0000 180

  2 omega   29.00   57.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481  -77.0000   30.0000 56

  3 omega   17.00  100.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481   57.0000  -90.0000 166

  4 omega   39.00   80.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481   57.0000  -30.0000 82

  5 omega   23.00   68.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481   57.0000 -150.0000 90

  6 omega   11.00   51.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481   57.0000 -180.0000 80

  7 omega  -39.00   22.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481  -77.0000   30.0000 122

  8 omega   25.00   52.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481   57.0000  120.0000 54

  9 phi    242.00  280.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
  31.1481   31.1481  -20.0000     -     76

 10 phi    317.00  359.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
  31.1481   31.1481  -20.0000     -     84

 11 phi    318.00  343.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
  31.1481   31.1481   60.0000     -     50

 12 omega  -18.00   63.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481  -80.0000  -81.6759 162

 13 omega    2.00   94.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481   30.0000  137.1092 184

 14 omega    1.00   48.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481   77.0000   60.0000 94

 15 omega  -18.00   61.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481  -77.0000   90.0000 158

 16 omega    1.00  100.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481   77.0000  -30.0000 198

 17 omega    1.00   30.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481   77.0000 -150.0000 58

 18 omega  -31.00   -3.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481  -77.0000  -30.0000 56

 19 omega   25.00   61.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481  -77.0000  -30.0000 72

 20 omega  -38.00   60.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       32.0000  -79.0000 -139.2153 196

 21 omega    6.00  104.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481   38.0000   90.0000 196

 22 omega  -39.00   61.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481  -77.0000  -60.0000 200

 23 omega  -41.00   57.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481  -38.0000  150.0000 196

 24 omega  -39.00   61.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481  -77.0000   60.0000 200

 25 omega  -40.00   63.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481  -80.0000 -163.9822 206

 26 omega    1.00  101.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481   77.0000   90.0000 200

 27 omega    1.00  101.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481   77.0000  -30.0000 200

 28 omega  -39.00   61.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481  -77.0000  120.0000 200

 29 omega    6.00  104.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481   38.0000 -120.0000 196

 30 omega  -39.00   61.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481  -77.0000  -30.0000 200

 31 omega    1.00  101.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481   77.0000 -180.0000 200

 32 omega    1.00  101.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481   77.0000   60.0000 200

 33 omega  -40.00   63.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481  -80.0000   27.6074 206

 34 omega    6.00  104.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481   38.0000    0.0000 196

 35 omega    1.00  101.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481   77.0000 -120.0000 200

 36 omega  -39.00   63.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       32.0000  -79.0000 -139.2153 204

 37 omega  -39.00   61.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481  -77.0000   90.0000 200

 38 omega  -39.00   61.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481  -77.0000  150.0000 200

 39 omega    2.00  104.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481   30.0000  137.1092 204

 40 phi    120.00  240.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
  31.1481   31.1481   20.0000     -     240

 41 omega  -42.00  104.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481    0.0000    0.0000 292

 42 omega  -42.00  104.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481    0.0000  120.0000 292

 43 omega  -42.00  104.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481    0.0000  240.0000 292

 44 phi      0.00  120.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
  40.0000   31.1481    0.0000     -     240

 45 phi      0.00  120.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
  31.1481   31.1481  -20.0000     -     240

 46 phi      0.00  120.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
  31.1481   31.1481   20.0000     -     240

 47 phi      0.00  120.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
  31.1481   31.1481  -40.0000     -     240

 48 phi      0.00  120.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
  31.1481   31.1481   40.0000     -     240

 49 phi      0.00  120.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
  31.1481   31.1481  -60.0000     -     240

 50 phi      0.00   25.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
  31.1481   31.1481   60.0000     -     50

 51 omega   11.00  100.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481   57.0000  -90.0000 178

 52 omega   37.00   63.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       32.0000  -79.0000  149.2164 52

 53 omega  -42.00  104.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481    0.0000  120.0000 292

 54 omega  -42.00  104.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481    0.0000  240.0000 292

 55 omega  -42.00  104.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481    0.0000    0.0000 292

 56 omega  -42.00  104.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481    0.0000  120.0000 292

 57 omega  -42.00  104.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       31.1481    0.0000  240.0000 292

 58 phi      0.00   88.00   0.5000    8.0000
omega____ theta____ kappa____ phi______ frames
  40.0000   31.1481    0.0000     -     176

;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w and \p scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_UB_11      -0.0234342000
_diffrn_orient_matrix_UB_12      0.0683577000
_diffrn_orient_matrix_UB_13      -0.0082108000
_diffrn_orient_matrix_UB_21      0.0445085000
_diffrn_orient_matrix_UB_22      -0.0001130000
_diffrn_orient_matrix_UB_23      -0.0340313000
_diffrn_orient_matrix_UB_31      -0.0465058000
_diffrn_orient_matrix_UB_32      -0.0053617000
_diffrn_orient_matrix_UB_33      -0.0189624000
_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  0.0725
_diffrn_reflns_av_unetI/netI     0.0291
_diffrn_reflns_laue_measured_fraction_full 0.998
_diffrn_reflns_laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            305972
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         34.488
_diffrn_reflns_theta_min         3.249
_diffrn_source                   'microfocus X-Ray tube'
_exptl_absorpt_coefficient_mu    2.820
_exptl_absorpt_correction_T_max  0.951
_exptl_absorpt_correction_T_min  0.591
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.537
_exptl_crystal_description       plate
_exptl_crystal_F_000             964
_exptl_crystal_size_max          0.2133
_exptl_crystal_size_mid          0.0665
_exptl_crystal_size_min          0.0177
_refine_diff_density_max         1.810
_refine_diff_density_min         -2.759
_refine_diff_density_rms         0.112
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.224
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     539
_refine_ls_number_reflns         16859
_refine_ls_number_restraints     54
_refine_ls_restrained_S_all      1.222
_refine_ls_R_factor_all          0.0364
_refine_ls_R_factor_gt           0.0333
_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^)+(0.0177P)^2^+2.4470P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0642
_refine_ls_wR_factor_ref         0.0650
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16163
_reflns_number_total             16859
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b02498_si_002.cif
_cod_data_source_block           ga_gp22
_cod_database_code               4344793
_audit_block_refno               2038
_audit_block_usercomment         'gp_jo_04 plate orange'
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         'C46 H46 Cl3 Hf1 N1 P2'
_chemical_oxdiff_usercomment     'gp_jo_04 plate orange'
_shelx_estimated_absorpt_t_max   0.766
_shelx_estimated_absorpt_t_min   0.766
_reflns_odcompleteness_completeness 99.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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 planarity
 C42B, C43B, C44B, C45B, C46B, C47B
 with sigma of 0.1
 C42A, C43A, C44A, C45A, C46A, C47A
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
C42A \\sim C42B \\sim C43B \\sim C44B \\sim C45B \\sim C45A \\sim C46B \\sim
C47B \\sim C43A \\sim C44A \\sim C46A \\sim C47A: within 1A with sigma of 0.04
and sigma for terminal atoms of 0.08
4. Same fragment restrains
{C42A, C43A, C44A, C45A, C46A, C47A}
as
{C42B, C43B, C44B, C45B, C46B, C47B}
5. Others
 Sof(C42B)=Sof(C43B)=Sof(H43B)=Sof(C44B)=Sof(H44B)=Sof(C45B)=Sof(H45B)=
 Sof(C46B)=Sof(H46B)=Sof(C47B)=Sof(H47B)=1-FVAR(1)
 Sof(C42A)=Sof(C43A)=Sof(H43A)=Sof(C44A)=Sof(H44A)=Sof(C45A)=Sof(H45A)=
 Sof(C46A)=Sof(H46A)=Sof(C47A)=Sof(H47A)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B)
6.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C9(H9), C11(H11), C25(H25), C26(H26), C27(H27), C28(H28),
 C29(H29), C31(H31), C32(H32), C33(H33), C34(H34), C35(H35), C37(H37), C38(H38),
  C39(H39), C40(H40), C41(H41), C43A(H43A), C44A(H44A), C45A(H45A), C46A(H46A),
 C47A(H47A), C43B(H43B), C44B(H44B), C45B(H45B), C46B(H46B), C47B(H47B)
6.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              12544
_cell_oxdiff_length_a            11.09282(10)
_cell_oxdiff_length_b            11.09294(9)
_cell_oxdiff_length_c            18.53238(15)
_cell_oxdiff_angle_alpha         76.9320(7)
_cell_oxdiff_angle_beta          77.1622(7)
_cell_oxdiff_angle_gamma         71.0505(8)
_cell_oxdiff_volume              2073.43(3)
_cell_oxdiff_measurement_reflns_used 96106