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_4344800
_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         'C60 H59 Hf N P2, 1.5(C7 H8)'
_chemical_formula_sum            'C70.5 H71 Hf N P2'
_chemical_formula_weight         1172.71
_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   mixed
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_gp24
_audit_creation_date
;
'Mon Sep 15 12:35:25 2014'
;
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
'21.10.2015 17:26:57 CEST UTC+02:00  encif 1.36'
_cell_angle_alpha                79.0795(4)
_cell_angle_beta                 89.6915(4)
_cell_angle_gamma                70.9254(4)
_cell_formula_units_Z            2
_cell_length_a                   10.16301(5)
_cell_length_b                   12.17106(6)
_cell_length_c                   25.05925(13)
_cell_measurement_reflns_used    163578
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      28.7010
_cell_measurement_theta_min      3.6520
_cell_volume                     2871.11(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34k (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,16:31:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34k (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,16:31:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34k (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,16:31:05)
;
_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      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 0.975
_diffrn_measurement_details
;
  1 omega   17.00   87.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   57.0000   90.0000 140

  2 omega    3.00   87.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   57.0000 -180.0000 168

  3 omega   -2.00   24.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   57.0000   30.0000 52

  4 omega  -20.00   49.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000 -150.0000 138

  5 omega  -52.00   49.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000   60.0000 202

  6 omega   -9.00   89.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   77.0000  -90.0000 196

  7 omega  -28.00   49.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000  120.0000 154

  8 omega  -17.00   49.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000    0.0000 132

  9 omega   -9.00   17.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000 -120.0000 52

 10 omega   24.00   49.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000 -120.0000 50

 11 omega   -9.00   26.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   77.0000   30.0000 70

 12 omega  -52.00   49.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000 -180.0000 202

 13 omega   46.00   72.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   57.0000 -150.0000 52

 14 omega   -5.00   37.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   38.0000   90.0000 84

 15 phi    213.00  238.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380  -40.0000     -     50

 16 omega  -39.00   50.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -79.0000  -52.0242 178

 17 omega  -50.00   40.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -57.0000  -60.0000 180

 18 omega   -3.00   87.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   57.0000 -120.0000 180

 19 omega  -50.00   40.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -57.0000 -180.0000 180

 20 omega  -50.00   40.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -57.0000   90.0000 180

 21 omega  -12.00   89.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   77.0000   90.0000 202

 22 omega  -52.00   49.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000  -30.0000 202

 23 omega  -52.00   49.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000  120.0000 202

 24 omega  -12.00   89.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   77.0000 -150.0000 202

 25 omega  -50.00   40.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -57.0000 -120.0000 180

 26 omega   -3.00   87.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   57.0000    0.0000 180

 27 omega  -52.00   49.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000   30.0000 202

 28 omega  -52.00   49.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000 -180.0000 202

 29 omega   -7.00   91.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   38.0000    0.0000 196

 30 omega  -54.00   91.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380    0.0000    0.0000 290

 31 omega  -54.00   91.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380    0.0000  120.0000 290

 32 omega  -54.00   91.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380    0.0000  240.0000 290

 33 phi      0.00  120.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  40.0000   18.5380    0.0000     -     240

 34 phi      0.00  120.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380  -20.0000     -     240

 35 phi      0.00  120.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380   20.0000     -     240

 36 phi      0.00  120.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380  -40.0000     -     240

 37 phi      0.00  120.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380   40.0000     -     240

 38 phi      0.00  120.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380  -60.0000     -     240

 39 phi      0.00  120.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380   60.0000     -     240

 40 phi    120.00  240.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  40.0000   18.5380    0.0000     -     240

 41 phi    120.00  240.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380  -20.0000     -     240

 42 omega  -47.00   50.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -79.0000  -52.0242 194

 43 phi    120.00  240.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380  -40.0000     -     240

 44 phi    120.00  240.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380   40.0000     -     240

 45 phi    120.00  240.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380  -60.0000     -     240

 46 phi    120.00  240.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380   60.0000     -     240

 47 phi    240.00  360.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  40.0000   18.5380    0.0000     -     240

 48 phi    240.00  360.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380  -20.0000     -     240

 49 phi    240.00  360.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380   20.0000     -     240

 50 phi    240.00  360.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380  -40.0000     -     240

 51 phi    240.00  360.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380   40.0000     -     240

 52 phi    240.00  360.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380  -60.0000     -     240

 53 phi    240.00  360.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380   60.0000     -     240

 54 omega  -26.00   92.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   19.0000 -180.0000 236

 55 phi    120.00  240.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380   20.0000     -     240

 56 omega  -26.00   92.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   19.0000 -120.0000 236

 57 omega  -26.00   92.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   19.0000  -90.0000 236

 58 omega  -26.00   92.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   19.0000  -60.0000 236

 59 omega  -26.00   92.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   19.0000  -30.0000 236

 60 omega  -26.00   92.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   19.0000    0.0000 236

 61 omega  -26.00   92.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   19.0000   30.0000 236

 62 omega  -26.00   92.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   19.0000   60.0000 236

 63 omega  -26.00   92.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   19.0000   90.0000 236

 64 omega  -26.00   16.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   19.0000  120.0000 84

 65 omega  -26.00   92.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   19.0000 -150.0000 236

;
_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      0.0106615000
_diffrn_orient_matrix_UB_12      -0.0060170000
_diffrn_orient_matrix_UB_13      0.0285031000
_diffrn_orient_matrix_UB_21      0.0626812000
_diffrn_orient_matrix_UB_22      0.0133171000
_diffrn_orient_matrix_UB_23      -0.0041006000
_diffrn_orient_matrix_UB_31      -0.0378296000
_diffrn_orient_matrix_UB_32      0.0611958000
_diffrn_orient_matrix_UB_33      -0.0022019000
_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  0.0592
_diffrn_reflns_av_unetI/netI     0.0216
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            371306
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.981
_diffrn_reflns_theta_min         3.318
_diffrn_source                   'microfocus X-Ray tube'
_exptl_absorpt_coefficient_mu    1.915
_exptl_absorpt_correction_T_max  0.844
_exptl_absorpt_correction_T_min  0.651
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34k (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,16:31:05)
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            'dark yellow'
_exptl_crystal_density_diffrn    1.356
_exptl_crystal_description       plate
_exptl_crystal_F_000             1206
_exptl_crystal_size_max          0.287
_exptl_crystal_size_mid          0.188
_exptl_crystal_size_min          0.111
_refine_diff_density_max         1.488
_refine_diff_density_min         -1.597
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.241
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     733
_refine_ls_number_reflns         14869
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.241
_refine_ls_R_factor_all          0.0320
_refine_ls_R_factor_gt           0.0302
_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^)+(0.0198P)^2^+3.6708P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0653
_refine_ls_wR_factor_ref         0.0658
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14466
_reflns_number_total             14869
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b02498_si_002.cif
_cod_data_source_block           ga_gp24
_cod_original_formula_sum        'C70.50 H71 Hf N P2'
_cod_database_code               4344800
_audit_block_refno               2148
_audit_block_usercomment         'gp_jo_81, plate, yellow'
_chemical_oxdiff_formula         'C70.5 H70.5 Hf N P2'
_chemical_oxdiff_usercomment     'gp_jo_81, plate, yellow'
_shelx_estimated_absorpt_t_max   0.832
_shelx_estimated_absorpt_t_min   0.832
_reflns_odcompleteness_completeness 99.80
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(H55C)=Sof(H55D)=Sof(C56B)=Sof(C57B)=Sof(H57B)=Sof(C58B)=Sof(H58B)=
 Sof(C59B)=Sof(H59B)=Sof(C60B)=Sof(H60B)=Sof(C61B)=Sof(H61B)=1-FVAR(1)
 Sof(H55A)=Sof(H55B)=Sof(C56A)=Sof(C57A)=Sof(H57A)=Sof(C58A)=Sof(H58A)=
 Sof(C59A)=Sof(H59A)=Sof(C60A)=Sof(H60A)=Sof(C61A)=Sof(H61A)=FVAR(1)
 Fixed Sof: C81(0.5) C82(0.5) H82(0.5) C83(0.5) H83(0.5) C84(0.5) H84(0.5)
 C85(0.5) H85(0.5) C86(0.5) H86(0.5) C87(0.5) H87A(0.5) H87B(0.5) H87C(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C48(H48A,H48B), C55(H55A,H55B), C55(H55C,H55D)
3.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), C43(H43), C44(H44), C45(H45), C46(H46),
 C47(H47), C50(H50), C51(H51), C52(H52), C53(H53), C54(H54), C57A(H57A),
 C58A(H58A), C59A(H59A), C60A(H60A), C61A(H61A), C57B(H57B), C58B(H58B),
 C59B(H59B), C60B(H60B), C61B(H61B), C82(H82), C83(H83), C84(H84), C85(H85),
 C86(H86), C72(H72), C73(H73), C74(H74), C75(H75), C76(H76)
3.c Fitted hexagon refined as free rotating group:
 C56A(C57A,C58A,C59A,C60A,C61A), C56B(C57B,C58B,C59B,C60B,C61B), C81(C82,C83,
 C84,C85,C86)
3.d 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), C87(H87A,H87B,H87C), C77(H77A,
 H77B,H77C)
;
_shelx_res_checksum              33109
_olex2_submission_special_instructions 'No special instructions were received'
_cell_oxdiff_length_a            10.16301(5)
_cell_oxdiff_length_b            12.17106(6)
_cell_oxdiff_length_c            25.05925(13)
_cell_oxdiff_angle_alpha         79.0795(4)
_cell_oxdiff_angle_beta          89.6915(4)
_cell_oxdiff_angle_gamma         70.9254(4)
_cell_oxdiff_volume              2871.11(2)
_cell_oxdiff_measurement_reflns_used 163578