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_4086554
_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 H47 N4 P Ti'
_chemical_formula_sum            'C42 H52 N4 O0.5 P Ti'
_chemical_formula_weight         699.74
_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     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ba_ms45
_audit_creation_date             2016-01-22
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
'22.01.2016 17:38:35 CET UTC+01:00  encif 1.38'
_cell_angle_alpha                102.6184(16)
_cell_angle_beta                 102.3519(15)
_cell_angle_gamma                110.2763(15)
_cell_formula_units_Z            2
_cell_length_a                   11.32651(18)
_cell_length_b                   13.3144(2)
_cell_length_c                   14.6393(3)
_cell_measurement_reflns_used    26876
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      70.4980
_cell_measurement_theta_min      4.3930
_cell_volume                     1917.05(7)
_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 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

--------------------------------------------------------------------------
  1  \w    -26.00  72.00   1.00    3.00    --    0.00  38.00 120.00   98
  2  \w    -72.00  26.00   1.00    3.00    --    0.00 -38.00-180.00   98
  3  \w    -21.00  69.00   1.00    3.00    --    0.00  57.00 -30.00   90
  4  \w    -26.00  72.00   1.00    3.00    --    0.00  38.00 -90.00   98
  5  \w    -37.00   6.00   1.00    3.00    --   14.00 115.00-176.29   43
  6  \w    -28.00   2.00   1.00    3.00    --   26.00 120.00 -20.33   30
  7  \w     -9.00  18.00   1.00   12.00    --   34.00 101.00 162.42   27
  8  \w     -2.00  24.00   1.00   12.00    --   38.00  96.00  84.26   26
  9  \w      5.00  32.00   1.00   12.00    --   42.00  90.00 -10.92   27
 10  \w     14.00  46.00   1.00   12.00    --   46.00  80.00  48.55   32
 11  \w     13.00  40.00   1.00   12.00    --   46.00  83.00-116.13   27
 12  \w     14.00  46.00   1.00   12.00    --   46.00  81.00   1.84   32
 13  \w     13.00  40.00   1.00   12.00    --   46.00  83.00 -80.35   27
 14  \w     12.00  38.00   1.00   12.00    --   46.00  84.00 141.61   26
 15  \w     12.00  38.00   1.00   12.00    --   46.00  84.00  99.02   26
 16  \w     19.00  47.00   1.00   12.00    --   50.00  79.00 158.03   28
 17  \w     18.00  46.00   1.00   12.00    --   50.00  81.00-175.47   28
 18  \w     24.00 124.00   1.00   12.00    --   54.00  77.00  80.78  100
 19  \w     24.00 124.00   1.00   12.00    --   54.00  77.00 -52.27  100
 20  \w    -15.00  75.00   1.00   12.00    --   54.00 -57.00  60.00   90
 21  \w     24.00 124.00   1.00   12.00    --   54.00  77.00 120.00  100
 22  \w     24.00 124.00   1.00   12.00    --   54.00  77.00-120.00  100
 23  \w     23.00  49.00   1.00   12.00    --   54.00  78.00  48.77   26
 24  \w      1.00  96.00   1.00   12.00    --   54.00 -99.00-150.00   95
 25  \w     23.00 111.00   1.00   12.00    --   54.00-125.00-120.00   88
 26  \w     24.00 124.00   1.00   12.00    --   54.00  77.00 -30.00  100
 27  \w     24.00 124.00   1.00   12.00    --   54.00  77.00 -90.00  100
 28  \w     24.00 124.00   1.00   12.00    --   54.00  77.00-150.00  100
 29  \w     23.00 111.00   1.00   12.00    --   54.00-125.00  60.00   88
 30  \w     28.00 128.00   1.00   12.00    --   58.00  77.00  16.51  100
 31  \w     29.00 128.00   1.00   12.00    --   58.00  76.00  -1.85   99
 32  \w     30.00 127.00   1.00   12.00    --   58.00  73.00 148.04   97
 33  \w     30.00 128.00   1.00   12.00    --   58.00  74.00 102.83   98
 34  \w     28.00 128.00   1.00   12.00    --   58.00  77.00-115.00  100
 35  \w     30.00 128.00   1.00   12.00    --   58.00  74.00-179.13   98
 36  \w     33.00  81.00   1.00   12.00    --   62.00  75.00 -21.67   48
 37  \w     44.00  78.00   1.00   12.00    --   62.00  61.00  37.45   34
 38  \w     43.00  72.00   1.00   12.00    --   66.00  67.00  -0.01   29
 39  \w    107.00 133.00   1.00   12.00    --   66.00  46.00-155.84   26
 40  \w     43.00  69.00   1.00   12.00    --   66.00  46.00-155.84   26
 41  \w     37.00 131.00   1.00   12.00    --   66.00  75.00 113.61   94
 42  \w     37.00  63.00   1.00   12.00    --   66.00  76.00 -79.94   26
 43  \w     40.00  66.00   1.00   12.00    --   66.00  76.00-109.51   26
 44  \w     36.00  62.00   1.00   12.00    --   66.00  77.00-167.23   26
 45  \w     48.00  74.00   1.00   12.00    --   70.00  62.00  77.41   26
 46  \w     48.00  73.00   1.00   12.00    --   70.00  64.00 -89.20   25
 47  \w     57.00  84.00   1.00   12.00    --   70.00  56.00 -41.31   27
 48  \w     63.00 132.00   1.00   12.00    --   70.00  58.00 149.59   69
 49  \w     50.00 142.00   1.00   12.00    --   74.00  68.00  33.62   92
 50  \w     50.00  85.00   1.00   12.00    --   74.00  68.00  83.49   35
 51  \w     47.00  75.00   1.00   12.00    --   74.00  71.00-136.52   28
 52  \w     52.00  78.00   1.00   12.00    --   74.00  61.00 -58.86   26
 53  \w     53.00  85.00   1.00   12.00    --   78.00  40.00-152.93   32
 54  \w     50.00  77.00   1.00   12.00    --   78.00  74.00  -5.45   27
 55  \w     56.00 114.00   1.00   18.00    --   82.00  70.00 -12.11   58
 56  \w     60.00  87.00   1.00   18.00    --   82.00  50.00 -11.68   27
 57  \w     60.00  87.00   1.00   18.00    --   86.00  35.00-121.74   27
 58  \w     77.00 104.00   1.00   18.00    --   86.00  56.00-129.88   27
 59  \w     66.00 102.00   1.00   18.00    --   86.00  65.00 -78.87   36
 60  \w     64.00  90.00   1.00   18.00    --   86.00  61.00-142.67   26
 61  \w     59.00  85.00   1.00   18.00    --   86.00  72.00 114.53   26
 62  \w     66.00  91.00   1.00   18.00    --   86.00  60.00-103.46   25
 63  \w    115.00 159.00   1.00   18.00    --   90.00  74.00  61.91   44
 64  \w     63.00  88.00   1.00   18.00    --   90.00  74.00  61.91   25
 65  \w     61.00  87.00   1.00   18.00    --   90.00  76.00-112.16   26
 66  \w     67.00 107.00   1.00   18.00    --   90.00  69.00 -57.55   40
 67  \w     75.00 111.00   1.00   18.00    --   94.00  59.00 106.37   36
 68  \w    119.00 167.00   1.00   18.00    --   98.00  73.00 100.64   48
 69  \w     70.00  96.00   1.00   18.00    --   98.00  73.00 100.64   26
 70  \w     77.00 159.00   1.00   18.00    --  102.00  70.00  48.74   82
 71  \w     74.00 149.00   1.00   18.00    --  102.00  74.00  31.38   75
 72  \w     79.00 108.00   1.00   18.00    --  108.00  77.00 120.00   29
 73  \w     81.00 108.00   1.00   18.00    --  108.00  77.00-150.00   27
 74  \w     82.00 111.00   1.00   18.00    --  108.00  38.00   0.00   29
 75  \w     94.00 129.00   1.00   18.00    --  108.00 -64.00  60.00   35
 76  \w     41.00  89.00   1.00   18.00    --  108.00 -64.00  60.00   48
 77  \w     49.00 116.00   1.00   18.00    --  108.00-111.00-120.00   67
 78  \w     37.00 116.00   1.00   18.00    --  108.00-111.00  60.00   79
 79  \w     82.00 109.00   1.00   18.00    --  108.00  38.00  30.00   27
 80  \w     83.00 113.00   1.00   18.00    --  108.00  38.00-180.00   30
 81  \w     86.00 175.00   1.00   18.00    --  108.00  64.00 -30.00   89
 82  \w     86.00 113.00   1.00   18.00    --  108.00  64.00-120.00   27
 83  \w     79.00 177.00   1.00   18.00    --  108.00  77.00  90.00   98
 84  \w     85.00 173.00   1.00   18.00    --  108.00  64.00-150.00   88
 85  \w     85.00 111.00   1.00   18.00    --  108.00  64.00 120.00   26
 86  \w    134.00 174.00   1.00   18.00    --  108.00  64.00-180.00   40
 87  \w     85.00 131.00   1.00   18.00    --  108.00  64.00-180.00   46
 88  \w     78.00 176.00   1.00   18.00    --  108.00  77.00 -90.00   98
 89  \w     86.00 111.00   1.00   18.00    --  108.00  64.00   0.00   25
 90  \w     41.00 136.00   1.00   18.00    --  108.00 -77.00-120.00   95
 91  \w     78.00 178.00   1.00   18.00    --  108.00  77.00  60.00  100
 92  \w    112.00 148.00   1.00   18.00    --  108.00  77.00 -60.00   36
 93  \w     78.00 107.00   1.00   18.00    --  108.00  77.00 -60.00   29
 94  \w     79.00 106.00   1.00   18.00    --  108.00  77.00-180.00   27
 95  \w     78.00 104.00   1.00   18.00    --  108.00  77.00 -30.00   26
 96  \w    101.00 145.00   1.00   18.00    --  108.00 -92.00  60.00   44
 97  \w     46.00  72.00   1.00   18.00    --  108.00 -92.00  60.00   26
 98  \w     80.00 106.00   1.00   18.00    --  108.00-111.00 -30.00   26
 99  \w    113.00 163.00   1.00   18.00    --  108.00  77.00 150.00   50
100  \w     78.00 106.00   1.00   18.00    --  108.00  77.00 150.00   28
101  \w     78.00 169.00   1.00   18.00    --  108.00  77.00-120.00   91
102  \w     79.00 173.00   1.00   18.00    --  108.00  77.00   0.00   94
103  \w     85.00 111.00   1.00   18.00    --  108.00  64.00 -60.00   26
104  \w    117.00 165.00   1.00   18.00    --  108.00  77.00 120.00   48
;
_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      -0.0331785000
_diffrn_orient_matrix_UB_12      -0.1262043000
_diffrn_orient_matrix_UB_13      -0.0452905000
_diffrn_orient_matrix_UB_21      -0.1471068000
_diffrn_orient_matrix_UB_22      -0.0237282000
_diffrn_orient_matrix_UB_23      -0.0432469000
_diffrn_orient_matrix_UB_31      0.0249470000
_diffrn_orient_matrix_UB_32      0.0212617000
_diffrn_orient_matrix_UB_33      -0.0948763000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0245
_diffrn_reflns_av_unetI/netI     0.0160
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            46804
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.746
_diffrn_reflns_theta_min         3.735
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.549
_exptl_absorpt_correction_T_max  0.846
_exptl_absorpt_correction_T_min  0.721
_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            orange
_exptl_crystal_density_diffrn    1.212
_exptl_crystal_description       block
_exptl_crystal_F_000             746
_exptl_crystal_size_max          0.159
_exptl_crystal_size_mid          0.089
_exptl_crystal_size_min          0.088
_refine_diff_density_max         0.295
_refine_diff_density_min         -0.344
_refine_diff_density_rms         0.038
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     423
_refine_ls_number_reflns         7290
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0311
_refine_ls_R_factor_gt           0.0291
_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^)+(0.0409P)^2^+0.7746P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0784
_refine_ls_wR_factor_ref         0.0795
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6888
_reflns_number_total             7290
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00384_si_002.cif
_cod_data_source_block           ba_ms45_sq
_cod_depositor_comments
'Adding full bibliography for 4086549--4086572.cif.'
_cod_original_cell_volume        1917.05(6)
_cod_original_formula_sum        'C42 H52 N4 O0.50 P Ti'
_cod_database_code               4086554
_audit_block_refno               2632
_audit_block_usercomment         'MS658, block, orange'
_shelx_estimated_absorpt_t_max   0.785
_shelx_estimated_absorpt_t_min   0.785
_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)
2.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,
 H40B,H40C)
;
_shelx_res_checksum              7502
_olex2_submission_special_instructions 'No special instructions were received'
_cell_oxdiff_length_a            11.32651(18)
_cell_oxdiff_length_b            13.3144(2)
_cell_oxdiff_length_c            14.6393(3)
_cell_oxdiff_angle_alpha         102.6184(16)
_cell_oxdiff_angle_beta          102.3519(15)
_cell_oxdiff_angle_gamma         110.2763(15)
_cell_oxdiff_volume              1917.05(6)
_cell_oxdiff_measurement_reflns_used 26876
_oxdiff_exptl_absorpt_empirical_full_min 0.768
_oxdiff_exptl_absorpt_empirical_full_max 1.300
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_theta     66.97
_reflns_odcompleteness_iscentric 1
_platon_squeeze_void_probe_radius 1.20