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_4086566
_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         'C46 H41 N2 P Zr'
_chemical_formula_sum            'C53 H49 N2 P Zr'
_chemical_formula_weight         836.13
_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_sb59
_audit_creation_date             2016-04-22
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.16 svn.r3265 for OlexSys, GUI svn.r5155)
;
_audit_update_record
'22.04.2016 17:46:00 CEST UTC+02:00  encif 1.45'
_cell_angle_alpha                67.695(2)
_cell_angle_beta                 86.916(2)
_cell_angle_gamma                86.495(2)
_cell_formula_units_Z            2
_cell_length_a                   10.2300(3)
_cell_length_b                   13.3848(3)
_cell_length_c                   16.6135(3)
_cell_measurement_reflns_used    11353
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      30.3970
_cell_measurement_theta_min      3.1780
_cell_volume                     2099.53(9)
_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    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_environment      perfluoro
_diffrn_ambient_temperature      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9241
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

--------------------------------------------------------------------------
  1  \w    -46.00 -21.00   0.50   17.50    --    4.00 113.00  26.27   50
  2  \w    -43.00  19.00   0.50   17.50    --   27.02 -80.00  61.31  124
  3  \w      2.00  35.00   0.50   17.50    --   27.02  38.00-180.00   66
  4  \w    -43.00  59.00   0.50   17.50    --   27.02 -80.00-159.94  204
  5  \w     -3.00  85.00   0.50   17.50    --   27.02  77.00 150.00  176
  6  \w     -4.00  24.00   0.50   17.50    --   27.02  80.00-118.60   56
  7  \w     33.00  59.00   0.50   17.50    --   27.02 -80.00  61.31   52
  8  \w     -2.00  90.00   0.50   17.50    --   27.02  77.00  30.00  184
  9  \w      8.00  95.00   0.50   17.50    --   27.02  57.00 -90.00  174
 10  \w     41.00  96.00   0.50   17.50    --   27.02  57.00 -30.00  110
 11  \w    -43.00  59.00   0.50   17.50    --   27.02 -80.00 -42.89  204
 12  \w    -43.00  -3.00   0.50   17.50    --   27.02 -76.00  22.00   80
 13  \w     22.00  57.00   0.50   17.50    --   27.02 -76.00  22.00   70
 14  \w     18.00  45.00   0.50   17.50    --   27.02  57.00 120.00   54
 15  \w     19.00  56.00   0.50   17.50    --   27.02 -77.00-120.00   74
 16  \w      8.00  47.00   0.50   17.50    --   27.02  77.00 -60.00   78
 17  \w    -42.00   2.00   0.50   17.50    --   27.02 -77.00 -90.00   88
 18  \w     29.00  56.00   0.50   17.50    --   27.02 -77.00 -90.00   54
 19  \w    -28.00  59.00   0.50   17.50    --   28.00 -79.00 116.14  174
;
_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      -0.0538531000
_diffrn_orient_matrix_UB_12      -0.0322807000
_diffrn_orient_matrix_UB_13      0.0028710000
_diffrn_orient_matrix_UB_21      -0.0236426000
_diffrn_orient_matrix_UB_22      0.0077273000
_diffrn_orient_matrix_UB_23      0.0382410000
_diffrn_orient_matrix_UB_31      -0.0370349000
_diffrn_orient_matrix_UB_32      0.0467491000
_diffrn_orient_matrix_UB_33      -0.0257156000
_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  0.0591
_diffrn_reflns_av_unetI/netI     0.0541
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            50443
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.536
_diffrn_reflns_theta_min         3.051
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.339
_exptl_absorpt_correction_T_max  0.974
_exptl_absorpt_correction_T_min  0.948
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.323
_exptl_crystal_description       irregular
_exptl_crystal_F_000             872
_exptl_crystal_size_max          0.199
_exptl_crystal_size_mid          0.128
_exptl_crystal_size_min          0.090
_refine_diff_density_max         0.748
_refine_diff_density_min         -0.827
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     488
_refine_ls_number_reflns         12819
_refine_ls_number_restraints     72
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0603
_refine_ls_R_factor_gt           0.0419
_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^)+(0.0459P)^2^+0.4483P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0942
_refine_ls_wR_factor_ref         0.1027
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10056
_reflns_number_total             12819
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00384_si_002.cif
_cod_data_source_block           ba_sb59_sq
_cod_depositor_comments
'Adding full bibliography for 4086549--4086572.cif.'
_cod_database_code               4086566
_audit_block_refno               2707
_audit_block_usercomment         'sb387, irregular, yellow'
_chemical_oxdiff_formula         'C46 H41 N2 P Zr C7 H8'
_chemical_oxdiff_usercomment     'sb387, irregular, yellow'
_shelx_estimated_absorpt_t_max   0.967
_shelx_estimated_absorpt_t_min   0.967
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_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
2. Rigid body (RIGU) restrains
 C27A, C28A, C29A, C30A, C31A, C32A, C27B, C28B, C29B, C30B, C31B, C32B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Sof(C27B)=Sof(C28B)=Sof(H28B)=Sof(C29B)=Sof(H29B)=Sof(C30B)=Sof(H30B)=
 Sof(C31B)=Sof(H31B)=Sof(C32B)=Sof(H32B)=1-FVAR(1)
 Sof(C27A)=Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30A)=
 Sof(C31A)=Sof(H31A)=Sof(C32A)=Sof(H32A)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C14(H14A,H14B), C40(H40A,H40B)
4.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), C35(H35), C36(H36), C37(H37), C38(H38), C39(H39),
 C42(H42), C43(H43), C44(H44), C45(H45), C46(H46), C28A(H28A), C29A(H29A),
 C30A(H30A), C31A(H31A), C32A(H32A), C28B(H28B), C29B(H29B), C30B(H30B),
 C31B(H31B), C32B(H32B)
4.c Fitted hexagon refined as free rotating group:
 C27A(C28A,C29A,C30A,C31A,C32A), C27B(C28B,C29B,C30B,C31B,C32B)
;
_shelx_res_checksum              53692
_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 1.484
_oxdiff_exptl_absorpt_empirical_full_min 0.779
_cell_oxdiff_length_a            10.2300(3)
_cell_oxdiff_length_b            13.3848(3)
_cell_oxdiff_length_c            16.6135(3)
_cell_oxdiff_angle_alpha         67.695(2)
_cell_oxdiff_angle_beta          86.916(2)
_cell_oxdiff_angle_gamma         86.495(2)
_cell_oxdiff_volume              2099.53(9)
_cell_oxdiff_measurement_reflns_used 11353
_platon_squeeze_void_probe_radius 1.20