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_4344788
_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_absolute_configuration ad
_chemical_formula_moiety         'C34 H54 Cl3 N P2 Ti'
_chemical_formula_sum            'C34 H54 Cl3 N P2 Ti'
_chemical_formula_weight         692.97
_chemical_properties_physical    air-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   mixed
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_gp31
_audit_creation_date
;
'Sat Apr 25 18:36:08 2015'
;
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;
Olex2 1.2
(compiled 2015.01.26 svn.r3151 for OlexSys, GUI svn.r4998)
;
_audit_update_record
'25.04.2015 18:38:43 CEST UTC+02:00  encif 1.29'
_cell_angle_alpha                90
_cell_angle_beta                 99.6850(9)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.65484(12)
_cell_length_b                   11.54401(12)
_cell_length_c                   13.13616(12)
_cell_measurement_reflns_used    53940
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      32.2380
_cell_measurement_theta_min      3.7800
_cell_volume                     1891.68(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35g (release 09-12-2014 CrysAlis171 .NET)
(compiled Dec  9 2014,15:38:47)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35g (release 09-12-2014 CrysAlis171 .NET)
(compiled Dec  9 2014,15:38:47)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35g (release 09-12-2014 CrysAlis171 .NET)
(compiled Dec  9 2014,15:38:47)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
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'encif (Wadepohl, 2009-14); encifer 1.5 (CCDC, 2014)'
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_diffrn_ambient_environment      'perfluoro polyether oil / N~2~'
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_diffrn_measured_fraction_theta_max 0.965
_diffrn_measurement_details
;
  1 omega  -42.00   58.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662  -79.0000 -168.0881 200

  2 omega  -43.00   59.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662  -80.0000   36.1312 204

  3 omega  -44.00   59.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662  -80.0000   99.6982 206

  4 omega   -3.00   25.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   79.0000   92.6149 56

  5 omega   -3.00   95.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   77.0000  -60.0000 196

  6 omega   17.00   43.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   57.0000  -90.0000 52

  7 omega   13.00   38.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   38.0000 -180.0000 50

  8 omega   45.00   83.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   38.0000 -180.0000 76

  9 omega    1.00   97.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   77.0000   30.0000 192

 10 omega    1.00   76.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   77.0000 -180.0000 150

 11 omega   -2.00   30.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662  -57.0000   90.0000 64

 12 omega  -37.00   57.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662  -79.0000  -83.6865 188

 13 omega    2.00   51.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   38.0000  -60.0000 98

 14 omega   19.00   57.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662  -77.0000  150.0000 76

 15 omega    6.00   39.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   57.0000  150.0000 66

 16 omega    5.00   32.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   38.0000   90.0000 54

 17 omega  -42.00   59.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0000  -78.0000  -46.8434 202

 18 omega   -3.00   97.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   77.0000 -120.0000 200

 19 omega  -46.00   71.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662  -19.0000 -150.0000 234

 20 omega  -42.00   48.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662  -57.0000   90.0000 180

 21 omega   -3.00   97.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   77.0000  150.0000 200

 22 omega    6.00   96.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   57.0000   30.0000 180

 23 omega    6.00   96.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   57.0000  -30.0000 180

 24 omega    6.00   96.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   57.0000   90.0000 180

 25 omega  -43.00   57.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662  -77.0000 -120.0000 200

 26 omega  -43.00   57.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662  -77.0000   60.0000 200

 27 omega   -4.00   25.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   79.0000   92.6149 58

 28 omega    1.00   99.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   38.0000 -180.0000 196

 29 omega   -3.00   97.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   77.0000  -30.0000 200

 30 omega  -43.00   57.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662  -77.0000   90.0000 200

 31 omega  -42.00   59.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0000  -78.0000  -46.8434 202

 32 omega  -46.00  -21.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662    0.0000  120.0000 50

 33 omega  -46.00  100.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.8662    0.0000    0.0000 292

;
_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_UB_11      -0.0406997000
_diffrn_orient_matrix_UB_12      0.0416215000
_diffrn_orient_matrix_UB_13      -0.0159421000
_diffrn_orient_matrix_UB_21      0.0342497000
_diffrn_orient_matrix_UB_22      0.0290313000
_diffrn_orient_matrix_UB_23      -0.0291436000
_diffrn_orient_matrix_UB_31      -0.0200432000
_diffrn_orient_matrix_UB_32      -0.0346616000
_diffrn_orient_matrix_UB_33      -0.0435615000
_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  0.0452
_diffrn_reflns_av_unetI/netI     0.0259
_diffrn_reflns_laue_measured_fraction_full 0.998
_diffrn_reflns_laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            122634
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.949
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.680
_diffrn_reflns_theta_min         3.266
_diffrn_source                   'microfocus X-Ray tube'
_exptl_absorpt_coefficient_mu    0.545
_exptl_absorpt_correction_T_max  0.947
_exptl_absorpt_correction_T_min  0.916
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35g (release 09-12-2014 CrysAlis171 .NET)
(compiled Dec  9 2014,15:38:47)
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 blue'
_exptl_crystal_density_diffrn    1.217
_exptl_crystal_description       block
_exptl_crystal_F_000             736
_exptl_crystal_size_max          0.212
_exptl_crystal_size_mid          0.164
_exptl_crystal_size_min          0.127
_refine_diff_density_max         0.357
_refine_diff_density_min         -0.277
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 5662 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.013(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.124
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     408
_refine_ls_number_reflns         13181
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.124
_refine_ls_R_factor_all          0.0318
_refine_ls_R_factor_gt           0.0303
_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^)+(0.0328P)^2^+0.3574P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0696
_refine_ls_wR_factor_ref         0.0701
_reflns_Friedel_coverage         0.886
_reflns_friedel_fraction_full    0.999
_reflns_friedel_fraction_max     0.932
_reflns_number_gt                12838
_reflns_number_total             13181
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b02498_si_002.cif
_cod_data_source_block           ga_gp31
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4344788
_audit_block_refno               2419
_audit_block_usercomment         'gp-ll-33 blue block'
_chemical_oxdiff_formula         'C34 H54 Cl3 N1 P2 Ti1'
_chemical_oxdiff_usercomment     'gp-ll-33 blue block'
_shelx_estimated_absorpt_t_max   0.947
_shelx_estimated_absorpt_t_min   0.947
_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.a Ternary CH refined with riding coordinates:
 C24(H24), C27(H27), C30(H30), C33(H33)
2.b 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), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C31(H31A,H31B,H31C),
 C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C)
;
_shelx_res_checksum              73805
_olex2_submission_special_instructions 'No special instructions were received'
_cell_oxdiff_length_a            12.65839(12)
_cell_oxdiff_length_b            11.54199(11)
_cell_oxdiff_length_c            13.13473(11)
_cell_oxdiff_angle_alpha         90.0191(7)
_cell_oxdiff_angle_beta          99.6834(7)
_cell_oxdiff_angle_gamma         89.9169(8)
_cell_oxdiff_volume              1891.68(3)
_cell_oxdiff_measurement_reflns_used 53940