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_4086564
_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         'C40 H49 Hf N2 P Si2, C4 H10 O'
_chemical_formula_sum            'C44 H59 Hf N2 O P Si2'
_chemical_formula_weight         897.57
_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   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_block_code                ba_sb48
_audit_creation_date             2016-02-26
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.16 svn.r3265 for OlexSys, GUI svn.r5155)
;
_audit_update_record
'26.02.2016 15:01:29 CET UTC+01:00  encif 1.38'
_cell_angle_alpha                69.808(2)
_cell_angle_beta                 84.7664(16)
_cell_angle_gamma                85.5702(15)
_cell_formula_units_Z            4
_cell_length_a                   14.1757(2)
_cell_length_b                   16.0067(3)
_cell_length_c                   20.6655(5)
_cell_measurement_reflns_used    31394
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      31.5580
_cell_measurement_theta_min      3.2630
_cell_volume                     4377.34(16)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41p (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41p (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41p (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    'SHELXT (Sheldrick, 2013)'
_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 0.966
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

--------------------------------------------------------------------------
  1  \w     -3.00  97.00   0.50   20.00    --   27.02  77.00 -90.00  200
  2  \w      7.00  96.00   0.50   20.00    --   27.02  57.00  30.00  178
  3  \w    -20.00  69.00   0.50   20.00    --   27.02 -99.00 120.00  178
  4  \w    -42.00  48.00   0.50   20.00    --   27.02 -57.00   0.00  180
  5  \w      7.00  96.00   0.50   20.00    --   27.02  57.00 120.00  178
  6  \w    -42.00  48.00   0.50   20.00    --   27.02 -57.00 150.00  180
  7  \w      7.00  96.00   0.50   20.00    --   27.02  57.00-120.00  178
  8  \w    -20.00  69.00   0.50   20.00    --   27.02 -99.00 -30.00  178
  9  \w     -3.00  97.00   0.50   20.00    --   27.02  77.00  60.00  200
 10  \w    -20.00  69.00   0.50   20.00    --   27.02 -99.00-120.00  178
 11  \w      2.00  99.00   0.50   20.00    --   27.02  38.00 -30.00  194
 12  \w     -3.00  97.00   0.50   20.00    --   27.02  77.00 150.00  200
 13  \w     -3.00  97.00   0.50   20.00    --   27.02  77.00 -30.00  200
 14  \w    -20.00  44.00   0.50   20.00    --   27.02 -99.00  90.00  128
 15  \w      6.00  60.00   0.50   20.00    --   27.02  38.00 120.00  108
 16  \w     57.00  96.00   0.50   20.00    --   27.02  57.00 -60.00   78
 17  \w     27.00  54.00   0.50   20.00    --   27.02  57.00  60.00   54
 18  \w     35.00  69.00   0.50   20.00    --   27.02 -99.00  30.00   68
 19  \w    -34.00   6.00   0.50   20.00    --   27.02 -77.00 -90.00   80
;
_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      0.0082988000
_diffrn_orient_matrix_UB_12      0.0075743000
_diffrn_orient_matrix_UB_13      0.0308106000
_diffrn_orient_matrix_UB_21      -0.0455566000
_diffrn_orient_matrix_UB_22      0.0217481000
_diffrn_orient_matrix_UB_23      -0.0001649000
_diffrn_orient_matrix_UB_31      -0.0196574000
_diffrn_orient_matrix_UB_32      -0.0412822000
_diffrn_orient_matrix_UB_33      0.0198615000
_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  0.055
_diffrn_reflns_av_unetI/netI     0.0866
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            194948
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.377
_diffrn_reflns_theta_min         2.983
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.508
_exptl_absorpt_correction_T_max  0.785
_exptl_absorpt_correction_T_min  0.482
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41p (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            colourless
_exptl_crystal_density_diffrn    1.362
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1840
_exptl_crystal_size_max          0.424
_exptl_crystal_size_mid          0.167
_exptl_crystal_size_min          0.116
_refine_diff_density_max         2.986
_refine_diff_density_min         -1.724
_refine_diff_density_rms         0.128
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.920
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     936
_refine_ls_number_reflns         43447
_refine_ls_number_restraints     33
_refine_ls_restrained_S_all      0.926
_refine_ls_R_factor_all          0.0542
_refine_ls_R_factor_gt           0.0345
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0302P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0666
_refine_ls_wR_factor_ref         0.0686
_reflns_Friedel_coverage         0.000
_reflns_number_gt                31629
_reflns_number_total             43447
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00384_si_002.cif
_cod_data_source_block           ba_sb48_5
_cod_depositor_comments
'Adding full bibliography for 4086549--4086572.cif.'
_cod_database_code               4086564
_audit_block_refno               2666
_audit_block_usercomment         'sb417b colourless needle'
_chemical_oxdiff_formula         'C40 H49 Hf1 N2 P1 Si2'
_chemical_oxdiff_usercomment     'sb417b colourless needle'
_shelx_estimated_absorpt_t_max   0.788
_shelx_estimated_absorpt_t_min   0.788
_shelxl_version_number           2014/7
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5087(3) 0.4913(3)
2. 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
3. Restrained distances
 O91-C91 \\sim O91-C93 \\sim O101-C101 \\sim O101-C103
 with sigma of 0.01
 C91-C92 \\sim C93-C94 \\sim C101-C102 \\sim C103-C104
 with sigma of 0.01
4. Rigid body (RIGU) restrains
 O101, C101, C102, C103, C104
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C11(H11A,H11B), C27(H27A,H27B), C34(H34A,H34B), C51(H51A,H51B),
 C61(H61A,H61B), C77(H77A,H77B), C84(H84A,H84B), C101(H10D,H10E), C103(H10I,
 H10J), C91(H91A,H91B), C93(H93A,H93B)
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C14(H14), C15(H15), C16(H16), C17(H17),
 C22(H22), C23(H23), C24(H24), C25(H25), C26(H26), C29(H29), C30(H30), C31(H31),
  C32(H32), C33(H33), C36(H36), C37(H37), C38(H38), C39(H39), C40(H40),
 C54(H54), C55(H55), C56(H56), C57(H57), C64(H64), C65(H65), C66(H66), C67(H67),
  C72(H72), C73(H73), C74(H74), C75(H75), C76(H76), C79(H79), C80(H80),
 C81(H81), C82(H82), C83(H83), C86(H86), C87(H87), C88(H88), C89(H89), C90(H90)
5.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C58(H58A,H58B,H58C), C59(H59A,H59B,
 H59C), C60(H60A,H60B,H60C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C70(H70A,
 H70B,H70C), C102(H10F,H10G,H10H), C104(H10K,H10L,H10M), C92(H92A,H92B,H92C),
 C94(H94A,H94B,H94C)
;
_shelx_res_checksum              9183
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.199
_oxdiff_exptl_absorpt_empirical_full_min 0.744
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
_twin_special_details
;
Component 2 rotated by 179.9950\%
 around [0.99 0.09 0.13] (reciprocal) or [1.00 0.00 -0.00] (direct)
;
_cell_oxdiff_length_a            14.1757(2)
_cell_oxdiff_length_b            16.0067(3)
_cell_oxdiff_length_c            20.6655(5)
_cell_oxdiff_angle_alpha         69.808(2)
_cell_oxdiff_angle_beta          84.7664(16)
_cell_oxdiff_angle_gamma         85.5702(15)
_cell_oxdiff_volume              4377.34(15)
_cell_oxdiff_measurement_reflns_used 31394