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_4344792
_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 N P2 Zr'
_chemical_formula_sum            'C46 H46 Cl3 N P2 Zr'
_chemical_formula_weight         872.35
_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_gp23
_audit_creation_date
;
'Fri Jul 11 11:29:04 2014'
;
_audit_update_record             'Fri Jul 11 11:31:38 CEST 2014'
_cell_angle_alpha                76.9709(13)
_cell_angle_beta                 77.1365(13)
_cell_angle_gamma                71.1366(13)
_cell_formula_units_Z            2
_cell_length_a                   11.01348(15)
_cell_length_b                   11.11271(16)
_cell_length_c                   18.5400(3)
_cell_measurement_reflns_used    26451
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      29.0720
_cell_measurement_theta_min      3.5860
_cell_volume                     2064.18(6)
_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 0.937
_diffrn_measurement_details
;
  1 omega  -50.00    9.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505  -57.0000 -120.0000 118

  2 omega   -2.00   88.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505   57.0000   30.0000 180

  3 omega    2.00   81.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505   38.0000 -180.0000 158

  4 omega   -7.00   87.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505   77.0000 -120.0000 188

  5 omega   -7.00   41.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505   38.0000    0.0000 96

  6 omega  -54.00   42.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505  -38.0000    0.0000 192

  7 omega  -11.00   36.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505   77.0000  120.0000 94

  8 omega  -43.00   48.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505  -77.0000  150.0000 182

  9 omega   -7.00   61.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505  -99.0000  -60.0000 136

 10 omega  -83.00  -45.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.9286  136.0000  -20.0000 76

 11 omega   -7.00   91.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505   38.0000   30.0000 196

 12 omega   -7.00   91.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505   38.0000  -60.0000 196

 13 omega  -11.00   89.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505   77.0000 -180.0000 200

 14 omega  -20.00   61.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505  -99.0000   90.0000 162

 15 omega   35.00   95.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505  178.0000   60.0000 120

 16 omega  -88.00    2.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.9286  -57.0000   30.0000 180

 17 omega  -44.00   54.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.9286   38.0000  150.0000 196

 18 omega  -81.00  -29.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.9286  133.0000  161.0000 104

 19 omega  -20.00   14.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505  -99.0000   30.0000 68

 20 omega  -40.00   50.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.9286   57.0000  -30.0000 180

;
_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      -0.0183145000
_diffrn_orient_matrix_UB_12      -0.0298507000
_diffrn_orient_matrix_UB_13      -0.0242193000
_diffrn_orient_matrix_UB_21      -0.0290493000
_diffrn_orient_matrix_UB_22      -0.0365077000
_diffrn_orient_matrix_UB_23      0.0315756000
_diffrn_orient_matrix_UB_31      -0.0598175000
_diffrn_orient_matrix_UB_32      0.0495497000
_diffrn_orient_matrix_UB_33      -0.0004656000
_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  0.0380
_diffrn_reflns_av_unetI/netI     0.0286
_diffrn_reflns_laue_measured_fraction_full 0.998
_diffrn_reflns_laue_measured_fraction_max 0.937
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            63593
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.937
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.092
_diffrn_reflns_theta_min         3.253
_diffrn_source                   'microfocus X-Ray tube'
_exptl_absorpt_coefficient_mu    0.572
_exptl_absorpt_correction_T_max  0.982
_exptl_absorpt_correction_T_min  0.952
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.404
_exptl_crystal_description       irregular
_exptl_crystal_F_000             900
_exptl_crystal_size_max          0.2881
_exptl_crystal_size_mid          0.1207
_exptl_crystal_size_min          0.0757
_refine_diff_density_max         0.487
_refine_diff_density_min         -0.401
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.158
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     503
_refine_ls_number_reflns         10389
_refine_ls_number_restraints     426
_refine_ls_restrained_S_all      1.135
_refine_ls_R_factor_all          0.0436
_refine_ls_R_factor_gt           0.0381
_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^)+(0.0238P)^2^+1.8814P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0771
_refine_ls_wR_factor_ref         0.0791
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9636
_reflns_number_total             10389
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b02498_si_002.cif
_cod_data_source_block           ga_gp23
_cod_database_code               4344792
_audit_block_refno               2101
_audit_block_usercomment         'gp315, irregular, red'
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         'C46 H46 N1 P2 Zr1 Cl3'
_chemical_oxdiff_usercomment     'gp315, irregular, red'
_shelx_estimated_absorpt_t_max   0.945
_shelx_estimated_absorpt_t_min   0.945
_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. Uiso/Uaniso restraints and constraints
C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9 \\sim C10
\\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18
\\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26
\\sim C27 \\sim C28 \\sim C29 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40
\\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim
C30B \\sim C31B \\sim C32B \\sim C33B \\sim C34B \\sim C35B \\sim C30A \\sim
C31A \\sim C32A \\sim C33A \\sim C34A \\sim C35A: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
Uanis(C30A) = Uanis(C30B)
Uanis(C33A) = Uanis(C33B)
3. Others
 Sof(C30A)=Sof(C31A)=Sof(H31A)=Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(H33A)=
 Sof(C34A)=Sof(H34A)=Sof(C35A)=Sof(H35A)=1-FVAR(1)
 Sof(C30B)=Sof(C31B)=Sof(H31B)=Sof(C32B)=Sof(H32B)=Sof(C33B)=Sof(H33B)=
 Sof(C34B)=Sof(H34B)=Sof(C35B)=Sof(H35B)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B)
4.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), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41), C43(H43), C44(H44),
  C45(H45), C46(H46), C47(H47), C31B(H31B), C32B(H32B), C33B(H33B), C34B(H34B),
 C35B(H35B), C31A(H31A), C32A(H32A), C33A(H33A), C34A(H34A), C35A(H35A)
4.c Fitted hexagon refined as free rotating group:
 C30B(C31B,C32B,C33B,C34B,C35B), C30A(C31A,C32A,C33A,C34A,C35A)
4.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)
;
_shelx_res_checksum              40691
_olex2_submission_special_instructions 'No special instructions were received'
_cell_oxdiff_length_a            11.01348(15)
_cell_oxdiff_length_b            11.11271(16)
_cell_oxdiff_length_c            18.5400(3)
_cell_oxdiff_angle_alpha         76.9709(13)
_cell_oxdiff_angle_beta          77.1365(13)
_cell_oxdiff_angle_gamma         71.1366(13)
_cell_oxdiff_volume              2064.18(5)
_cell_oxdiff_measurement_reflns_used 26451