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_4086572
_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         'C68 H67 Hf N4 P, C2 H5 O0.5'
_chemical_formula_sum            'C70 H72 Hf N4 O0.5 P'
_chemical_formula_weight         1186.77
_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                ba_lm2
_audit_creation_date             2015-11-30
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
'30.11.2015 16:58:18 CET UTC+01:00  encif 1.36'
_cell_angle_alpha                107.3504(15)
_cell_angle_beta                 93.0867(11)
_cell_angle_gamma                95.0282(11)
_cell_formula_units_Z            2
_cell_length_a                   11.84756(13)
_cell_length_b                   12.4209(2)
_cell_length_c                   20.4206(3)
_cell_measurement_reflns_used    42244
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      32.1770
_cell_measurement_theta_min      3.6910
_cell_volume                     2847.14(7)
_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 0.944
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

--------------------------------------------------------------------------
  1  \w     -3.00  97.00   0.50   15.00    --   27.02  77.00   0.00  200
  2  \w      7.00  96.00   0.50   15.00    --   27.02  57.00 120.00  178
  3  \w    -45.00  53.00   0.50   15.00    --   27.02 -38.00  60.00  196
  4  \w      7.00  96.00   0.50   15.00    --   27.02  57.00 -30.00  178
  5  \w    -20.00  69.00   0.50   15.00    --   27.02 -99.00 150.00  178
  6  \w    -43.00  57.00   0.50   15.00    --   27.02 -77.00 -90.00  200
  7  \w     -3.00  97.00   0.50   15.00    --   27.02  77.00-180.00  200
  8  \w    -20.00  69.00   0.50   15.00    --   27.02 -99.00  60.00  178
  9  \w    -42.00  48.00   0.50   15.00    --   27.02 -57.00-180.00  180
 10  \w      8.00  42.00   0.50   15.00    --   27.02  77.00-120.00   68
 11  \w      4.00  75.00   0.50   15.00    --   27.02  38.00 120.00  142
 12  \w     -2.00  46.00   0.50   15.00    --   27.02  77.00  90.00   96
 13  \w     41.00  67.00   0.50   15.00    --   27.02 -99.00 -60.00   52
 14  \w      9.00  55.00   0.50   15.00    --   27.02  38.00 -60.00   92
 15  \w     64.00  90.00   0.50   15.00    --   27.02  57.00  30.00   52
 16  \w    -42.00  25.00   0.50   15.00    --   27.02 -57.00 -30.00  134
;
_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_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0073989000
_diffrn_orient_matrix_UB_12      -0.0422940000
_diffrn_orient_matrix_UB_13      0.0162717000
_diffrn_orient_matrix_UB_21      0.0321813000
_diffrn_orient_matrix_UB_22      -0.0283420000
_diffrn_orient_matrix_UB_23      -0.0269694000
_diffrn_orient_matrix_UB_31      0.0504717000
_diffrn_orient_matrix_UB_32      0.0320968000
_diffrn_orient_matrix_UB_33      0.0184818000
_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  0.0391
_diffrn_reflns_av_unetI/netI     0.0356
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.944
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            84075
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.944
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.393
_diffrn_reflns_theta_min         3.293
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.908
_exptl_absorpt_correction_T_max  0.949
_exptl_absorpt_correction_T_min  0.788
_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    1.384
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1222
_exptl_crystal_size_max          0.159
_exptl_crystal_size_mid          0.123
_exptl_crystal_size_min          0.029
_refine_diff_density_max         1.017
_refine_diff_density_min         -1.091
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     738
_refine_ls_number_reflns         19278
_refine_ls_number_restraints     23
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0319
_refine_ls_R_factor_gt           0.0280
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0221P)^2^+1.6463P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0575
_refine_ls_wR_factor_ref         0.0589
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17967
_reflns_number_total             19278
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00384_si_002.cif
_cod_data_source_block           ba_lm2
_cod_depositor_comments
'Adding full bibliography for 4086549--4086572.cif.'
_cod_original_cell_volume        2847.13(8)
_cod_original_formula_sum        'C70 H72 Hf N4 O0.50 P'
_cod_database_code               4086572
_audit_block_refno               2584
_audit_block_usercomment         'lm091 yellow irregular'
_chemical_oxdiff_formula         'C70 H72 Hf1 N4 O0.5 P1'
_chemical_oxdiff_usercomment     'lm091 yellow irregular'
_shelx_estimated_absorpt_t_max   0.832
_shelx_estimated_absorpt_t_min   0.832
_reflns_odcompleteness_completeness 99.81
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 O91-C92A \\sim O91-C92B
 with sigma of 0.01
 C92A-C93 \\sim C92B-C93
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C92A \\sim C92B: within 1A with sigma of 0.02 and sigma for terminal atoms of
0.02
4. Rigid body (RIGU) restrains
 O91, C92A, C92B, C93
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C92B)=Sof(H92A)=Sof(H92B)=Sof(H93D)=Sof(H93E)=Sof(H93F)=1-FVAR(1)
 Sof(C92A)=Sof(H92C)=Sof(H92D)=Sof(H93A)=Sof(H93B)=Sof(H93C)=FVAR(1)
 Fixed Sof: O91(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C92B(H92A,H92B), C92A(H92C,H92D)
6.b Me refined with riding coordinates:
 C93(H93D,H93E,H93F), C93(H93A,H93B,H93C)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C11(H11), C13(H13), C18(H18),
 C19(H19), C20(H20), C21(H21), C24(H24), C26(H26), C28(H28), C32(H32), C33(H33),
  C34(H34), C35(H35), C36(H36), C40(H40), C41(H41), C42(H42), C43(H43),
 C44(H44), C47(H47), C48(H48), C49(H49), C56(H56), C57(H57), C58(H58), C59(H59),
  C60(H60), C63(H63), C64(H64), C65(H65)
6.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C67(H67A,H67B,H67C), C68(H68A,
 H68B,H68C)
;
_shelx_res_checksum              58474
_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 1.122
_oxdiff_exptl_absorpt_empirical_full_min 0.892
_cell_oxdiff_length_a            11.84756(13)
_cell_oxdiff_length_b            12.4209(2)
_cell_oxdiff_length_c            20.4206(3)
_cell_oxdiff_angle_alpha         107.3504(15)
_cell_oxdiff_angle_beta          93.0867(11)
_cell_oxdiff_angle_gamma         95.0282(11)
_cell_oxdiff_volume              2847.13(7)
_cell_oxdiff_measurement_reflns_used 42244