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_4086569
_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         'C72 H70 N4 P2 Zr, C5 H12'
_chemical_formula_sum            'C77 H82 N4 P2 Zr'
_chemical_formula_weight         1216.62
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
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'Wed Jul 02 13:34:24 2014'
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Olex2 1.2
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'02.05.2016 14:39:43 CEST UTC+02:00  encif 1.45'
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_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
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_diffrn_ambient_environment      'perfluoro polyether oil / N~2~'
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;
  1 omega  -43.00   48.00   0.5000   28.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505  -80.0000   -5.0916 182

  2 omega  -44.00   48.00   0.5000   28.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505  -80.0000  164.3467 184

  3 omega   -6.00   76.00   0.5000   28.0000
omega____ theta____ kappa____ phi______ frames
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  4 omega    0.00   77.00   0.5000   28.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505   57.0000   60.0000 154

  5 omega    0.00   43.00   0.5000   28.0000
omega____ theta____ kappa____ phi______ frames
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  6 omega   63.00   89.00   0.5000   28.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505   50.0000  -89.0000 52

  7 omega   -9.00   82.00   0.5000   28.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505   77.0000  150.0000 182

  8 omega  -43.00   48.00   0.5000   28.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505  -80.0000  -99.7396 182

  9 omega  -43.00   47.00   0.5000   28.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505  -80.0000   70.2816 180

 10 omega  -54.00   44.00   0.5000   28.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505  -38.0000   30.0000 196

 11 omega  -50.00   40.00   0.5000   28.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505  -57.0000 -150.0000 180

 12 omega   -3.00   88.00   0.5000   28.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505   57.0000 -150.0000 182

 13 omega   -3.00   88.00   0.5000   28.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505   57.0000    0.0000 182

 14 omega  -46.00   -8.00   0.5000   28.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505  -80.0000  -57.7816 76

 15 omega   -3.00   88.00   0.5000   28.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8505   57.0000  120.0000 182

;
_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      0.0343922000
_diffrn_orient_matrix_UB_12      0.0065482000
_diffrn_orient_matrix_UB_13      0.0187479000
_diffrn_orient_matrix_UB_21      -0.0081604000
_diffrn_orient_matrix_UB_22      0.0464746000
_diffrn_orient_matrix_UB_23      0.0058672000
_diffrn_orient_matrix_UB_31      -0.0099489000
_diffrn_orient_matrix_UB_32      -0.0156304000
_diffrn_orient_matrix_UB_33      0.0252700000
_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  0.1074
_diffrn_reflns_av_unetI/netI     0.0543
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            141979
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.401
_diffrn_reflns_theta_min         3.256
_diffrn_source                   'microfocus X-Ray tube'
_exptl_absorpt_coefficient_mu    0.268
_exptl_absorpt_correction_T_max  0.986
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;
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
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Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
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_exptl_crystal_description       needle
_exptl_crystal_F_000             2568
_exptl_crystal_size_max          0.198
_exptl_crystal_size_mid          0.102
_exptl_crystal_size_min          0.061
_refine_diff_density_max         1.221
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_refine_ls_extinction_method     none
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_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     791
_refine_ls_number_reflns         13116
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      38.432
_refine_ls_R_factor_all          0.0965
_refine_ls_R_factor_gt           0.0881
_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^)+(0.0150P)^2^+25.3521P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1477
_refine_ls_wR_factor_ref         0.1512
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12267
_reflns_number_total             13116
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00384_si_002.cif
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_cod_depositor_comments
'Adding full bibliography for 4086549--4086572.cif.'
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               4086569
_audit_block_refno               2087
_audit_block_usercomment         'MS352, needle,yellow'
_chemical_oxdiff_formula         'C77 H82 N4 P2 Zr1'
_chemical_oxdiff_usercomment     'MS352, needle,yellow'
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.974
_reflns_odcompleteness_completeness 99.73
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
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_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. Restrained distances
 C91-C92 \\sim C2-C93 \\sim C93-C94 \\sim C94-C95
 with sigma of 0.005
3. Rigid body (RIGU) restrains
 C1, C92, C93, C94, C95
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4.a Secondary CH2 refined with riding coordinates:
 C92(H92A,H92B), C93(H93A,H93B), C94(H94A,H94B)
4.b 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), C39(H39), C40(H40), C41(H41), C42(H42),
 C45(H45), C47(H47), C49(H49), C54(H54), C55(H55), C56(H56), C57(H57), C60(H60),
  C61(H61), C62(H62), C63(H63), C64(H64), C66(H66), C68(H68), C70(H70)
4.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C71(H71A,H71B,H71C), C72(H72A,
 H72B,H72C), C91(H91A,H91B,H91C), C95(H95A,H95B,H95C)
;
_shelx_res_checksum              53951
_olex2_submission_special_instructions 'No special instructions were received'
_cell_oxdiff_length_a            20.2090(4)
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_cell_oxdiff_length_c            23.1847(5)
_cell_oxdiff_angle_alpha         90.0034(17)
_cell_oxdiff_angle_beta          107.0948(18)
_cell_oxdiff_angle_gamma         90.0431(17)
_cell_oxdiff_volume              6421.4(2)
_cell_oxdiff_measurement_reflns_used 17014