Closely Related Benzylene-Linked Diamidophosphine Scaffolds and Their Zirconium and Hafnium Complexes: How Small Changes of the Ligand Result in Different Complex Stabilities and Reactivities
Batke, Sonja; Sietzen, Malte; Merz, Lukas; Wadepohl, Hubert; Ballmann, Joachim; Organometallics 35 (2016) 2294–; doi:10.1021/acs.organomet.6b00384

data_4086570
_publ_section_title
;
 Closely Related Benzylene-Linked Diamidophosphine Scaffolds and Their
 Zirconium and Hafnium Complexes: How Small Changes of the Ligand Result
 in Different Complex Stabilities and Reactivities
;
_journal_issue                   13
_journal_name_full               Organometallics
_journal_page_first              2294
_journal_paper_doi               10.1021/acs.organomet.6b00384
_journal_volume                  35
_journal_year                    2016
_chemical_formula_moiety         'C64 H59 N4 P Zr'
_chemical_formula_sum            'C64 H59 N4 P Zr'
_chemical_formula_weight         1006.34
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ba_sb42
_audit_creation_date             2015-12-15
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
'15.12.2015 15:25:52 CET UTC+01:00  encif 1.38'
_cell_angle_alpha                90
_cell_angle_beta                 104.950(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.3382(3)
_cell_length_b                   13.3600(3)
_cell_length_c                   25.6716(5)
_cell_measurement_reflns_used    19307
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      26.9980
_cell_measurement_theta_min      3.5670
_cell_volume                     5082.52(19)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_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
_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 0.994
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

--------------------------------------------------------------------------
  1  \w    -20.00  61.00   0.50   15.00    --   18.77 -99.00 120.00  162
  2  \w    -54.00  44.00   0.50   15.00    --   18.77 -38.00 -60.00  196
  3  \w     -3.00  88.00   0.50   15.00    --   18.77  57.00 150.00  182
  4  \w    -51.00  49.00   0.50   15.00    --   18.77 -77.00 120.00  200
  5  \w      6.00  61.00   0.50   15.00    --   18.77 -99.00  30.00  110
  6  \w     35.00  61.00   0.50   15.00    --   18.77 -99.00-120.00   52
  7  \w     -3.00  35.00   0.50   15.00    --   18.77  57.00  60.00   76
  8  \w     40.00  67.00   0.50   15.00    --   18.77  57.00  60.00   54
  9  \w    -50.00  40.00   0.50   15.00    --   18.77 -57.00   0.00  180
 10  \w    -19.00  61.00   0.50   15.00    --   18.77 -99.00 -60.00  160
 11  \w    -16.00  11.00   0.50   15.00    --   18.77 -99.00-180.00   54
 12  \w     -9.00  67.00   0.50   15.00    --   18.77  77.00  90.00  152
 13  \w     28.00  61.00   0.50   15.00    --   18.77 -99.00 150.00   66
 14  \f    274.00 301.00   0.50   15.00  18.77  18.77  60.00    --    54
 15  \w    -35.00  39.00   0.50   15.00    --   18.77 -61.00-149.00  148
 16  \w     -2.00  25.00   0.50   15.00    --   18.77  61.00 -11.00   54
 17  \w     -3.00  90.00   0.50   15.00    --   18.77  38.00  30.00  186
 18  \w     -6.00  64.00   0.50   15.00    --   18.77  38.00 150.00  140
 19  \w    -11.00  85.00   0.50   15.00    --   18.77  77.00-120.00  192
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0141862000
_diffrn_orient_matrix_UB_12      -0.0506121000
_diffrn_orient_matrix_UB_13      -0.0034053000
_diffrn_orient_matrix_UB_21      0.0387656000
_diffrn_orient_matrix_UB_22      -0.0147171000
_diffrn_orient_matrix_UB_23      0.0202886000
_diffrn_orient_matrix_UB_31      -0.0242202000
_diffrn_orient_matrix_UB_32      0.0063418000
_diffrn_orient_matrix_UB_33      0.0198728000
_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  0.0920
_diffrn_reflns_av_unetI/netI     0.0506
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            115679
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.525
_diffrn_reflns_theta_min         3.345
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.294
_exptl_absorpt_correction_T_max  0.974
_exptl_absorpt_correction_T_min  0.955
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.315
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2104
_exptl_crystal_size_max          0.236
_exptl_crystal_size_mid          0.175
_exptl_crystal_size_min          0.137
_refine_diff_density_max         1.050
_refine_diff_density_min         -0.916
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.177
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     635
_refine_ls_number_reflns         11640
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.177
_refine_ls_R_factor_all          0.0877
_refine_ls_R_factor_gt           0.0673
_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^)+(0.0261P)^2^+11.6370P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1371
_refine_ls_wR_factor_ref         0.1449
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9231
_reflns_number_total             11640
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00384_si_002.cif
_cod_data_source_block           ba_sb42
_cod_depositor_comments
'Adding full bibliography for 4086549--4086572.cif.'
_cod_original_cell_volume        5082.51(19)
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               4086570
_audit_block_refno               2601
_audit_block_usercomment         'sb420, irregular, yellow'
_chemical_oxdiff_formula         'C64 H59 Zr N4 P'
_chemical_oxdiff_usercomment     'sb420, irregular, yellow'
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.971
_reflns_odcompleteness_completeness 99.71
_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 Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C14(H14A,H14B), C34(H34A,H34B), C50(H50A,H50B)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C17(H17), C18(H18), C19(H19), C20(H20), C22(H22), C23(H23), C24(H24),
  C25(H25), C26(H26), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32),
 C36(H36), C37(H37), C38(H38), C39(H39), C40(H40), C43(H43), C44(H44), C45(H45),
  C52(H52), C53(H53), C54(H54), C55(H55), C56(H56), C59(H59), C60(H60), C61(H61)
2.c Idealised Me refined as rotating group:
 C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C63(H63A,H63B,H63C), C64(H64A,H64B,
 H64C)
;
_shelx_res_checksum              77931
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.221
_oxdiff_exptl_absorpt_empirical_full_min 0.918
_cell_oxdiff_length_a            15.3404(3)
_cell_oxdiff_length_b            13.3607(3)
_cell_oxdiff_length_c            25.6683(5)
_cell_oxdiff_angle_alpha         90.0287(17)
_cell_oxdiff_angle_beta          104.9640(16)
_cell_oxdiff_angle_gamma         89.8591(17)
_cell_oxdiff_volume              5082.51(17)
_cell_oxdiff_measurement_reflns_used 19307