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_4086556
_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         'C36 H35 I2 N2 P Ti, C7 H8'
_chemical_formula_sum            'C43 H43 I2 N2 P Ti'
_chemical_formula_weight         920.46
_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_ms44
_audit_creation_date             2015-10-19
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
'19.10.2015 18:59:20 CEST UTC+02:00  encif 1.36'
_cell_angle_alpha                90
_cell_angle_beta                 96.3526(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.83406(11)
_cell_length_b                   13.50260(12)
_cell_length_c                   22.40089(18)
_cell_measurement_reflns_used    58185
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      28.6100
_cell_measurement_theta_min      3.5210
_cell_volume                     3858.09(6)
_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 0.977
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

--------------------------------------------------------------------------
  1  \w      0.00  84.00   0.50   10.00    --   19.75  38.00 -90.00  168
  2  \w      1.00  86.00   0.50   10.00    --   19.75  57.00   0.00  170
  3  \w    -47.00  38.00   0.50   10.00    --   19.75 -57.00-150.00  170
  4  \w    -46.00  39.00   0.50   10.00    --   19.75 -57.00 -30.00  170
  5  \w    -20.00  63.00   0.50   10.00    --   19.75 -99.00 150.00  166
  6  \w     -3.00  81.00   0.50   10.00    --   19.75  76.00 114.84  168
  7  \w     -2.00  89.00   0.50   10.00    --   19.75  57.00 120.00  182
  8  \w    -49.00  41.00   0.50   10.00    --   19.75 -57.00  90.00  180
  9  \w    -20.00  63.00   0.50   10.00    --   19.75 -99.00 -30.00  166
 10  \w    -12.00  91.00   0.50   10.00    --   19.75  77.00-120.00  206
 11  \w      6.00  81.00   0.50   10.00    --   19.75-130.00  86.14  150
 12  \w     -2.00  89.00   0.50   10.00    --   19.75  57.00-180.00  182
 13  \w    -20.00  63.00   0.50   10.00    --   19.75 -99.00-180.00  166
 14  \w    -20.00  63.00   0.50   10.00    --   19.75 -99.00  60.00  166
 15  \w    -12.00  91.00   0.50   10.00    --   19.75  77.00  90.00  206
 16  \w     -2.00  89.00   0.50   10.00    --   19.75  57.00  30.00  182
 17  \w    -69.00 -35.00   0.50   10.00    --    2.00 147.00  98.42   68
 18  \w    -62.00  36.00   0.50   10.00    --   10.00 -41.00 111.24  196
 19  \w    -42.00 -15.00   0.50   10.00    --   10.00 115.00-113.76   54
 20  \w    -12.00  91.00   0.50   10.00    --   19.75  77.00 -30.00  206
 21  \f    120.00 240.00   0.50   10.00  40.00  19.75   0.00    --   240
 22  \w    -54.00  43.00   0.50   10.00    --   18.00 -43.00 155.46  194
 23  \w     -2.00  89.00   0.50   10.00    --   19.75  57.00  60.00  182
 24  \w    -12.00  91.00   0.50   10.00    --   19.75  77.00  60.00  206
 25  \f      0.00 120.00   0.50   10.00  40.00  19.75   0.00    --   240
 26  \w    -20.00  63.00   0.50   10.00    --   19.75 -99.00-150.00  166
 27  \f      0.00 110.00   0.50   10.00  19.75  19.75  20.00    --   220
;
_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      0.0292652000
_diffrn_orient_matrix_UB_12      0.0126333000
_diffrn_orient_matrix_UB_13      0.0276757000
_diffrn_orient_matrix_UB_21      0.0117756000
_diffrn_orient_matrix_UB_22      -0.0507483000
_diffrn_orient_matrix_UB_23      0.0054512000
_diffrn_orient_matrix_UB_31      0.0457953000
_diffrn_orient_matrix_UB_32      0.0049484000
_diffrn_orient_matrix_UB_33      -0.0148102000
_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  0.0578
_diffrn_reflns_av_unetI/netI     0.0269
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.977
_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            173153
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.825
_diffrn_reflns_theta_min         3.375
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.896
_exptl_absorpt_correction_T_max  0.886
_exptl_absorpt_correction_T_min  0.768
_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            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.585
_exptl_crystal_description       block
_exptl_crystal_F_000             1832
_exptl_crystal_size_max          0.199
_exptl_crystal_size_mid          0.108
_exptl_crystal_size_min          0.089
_refine_diff_density_max         0.525
_refine_diff_density_min         -0.340
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     447
_refine_ls_number_reflns         9858
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0347
_refine_ls_R_factor_gt           0.0260
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0209P)^2^+2.7315P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0508
_refine_ls_wR_factor_ref         0.0533
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8561
_reflns_number_total             9858
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00384_si_002.cif
_cod_data_source_block           ba_ms44
_cod_depositor_comments
'Adding full bibliography for 4086549--4086572.cif.'
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               4086556
_audit_block_refno               2544
_audit_block_usercomment         'MS662, block, black'
_chemical_oxdiff_formula         'C43 H43 I2 N2 P1 Ti1'
_chemical_oxdiff_usercomment     'MS662, block, black'
_shelx_estimated_absorpt_t_max   0.833
_shelx_estimated_absorpt_t_min   0.833
_reflns_odcompleteness_completeness 99.75
_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:
 C7(H7A,H7B), C22(H22A,H22B)
2.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), C52(H52), C53(H53), C54(H54), C55(H55), C56(H56)
2.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C57(H57A,H57B,H57C)
;
_shelx_res_checksum              92403
_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 1.147
_oxdiff_exptl_absorpt_empirical_full_min 0.904
_cell_oxdiff_length_a            12.83389(8)
_cell_oxdiff_length_b            13.50258(9)
_cell_oxdiff_length_c            22.40103(12)
_cell_oxdiff_angle_alpha         89.9927(5)
_cell_oxdiff_angle_beta          96.3480(5)
_cell_oxdiff_angle_gamma         89.9762(5)
_cell_oxdiff_volume              3858.09(4)
_cell_oxdiff_measurement_reflns_used 58185