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_4086571
_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         'C49 H58 Hf N3 P Si2'
_chemical_formula_sum            'C49 H58 Hf N3 P Si2'
_chemical_formula_weight         954.62
_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_sb45
_audit_creation_date             2016-01-19
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
'19.01.2016 18:25:26 CET UTC+01:00  encif 1.38'
_cell_angle_alpha                98.1474(6)
_cell_angle_beta                 91.2024(7)
_cell_angle_gamma                98.6327(6)
_cell_formula_units_Z            4
_cell_length_a                   11.21305(9)
_cell_length_b                   17.74642(13)
_cell_length_c                   22.97468(19)
_cell_measurement_reflns_used    159344
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      70.5770
_cell_measurement_theta_min      3.8790
_cell_volume                     4470.18(6)
_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 0.991
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

--------------------------------------------------------------------------
  1  \w    -26.00  72.00   1.00    2.00    --    0.00  38.00  90.00   98
  2  \w    -30.00  70.00   1.00    2.00    --    0.00  77.00 -90.00  100
  3  \w    -69.00  21.00   1.00    2.00    --    0.00 -57.00 120.00   90
  4  \w    -21.00  69.00   1.00    2.00    --    0.00  57.00-120.00   90
  5  \w    -69.00  21.00   1.00    2.00    --    0.00 -57.00   0.00   90
  6  \w    -30.00  70.00   1.00    2.00    --    0.00  77.00  30.00  100
  7  \w    -69.00  21.00   1.00    2.00    --    0.00 -57.00-120.00   90
  8  \w    -37.00  11.00   1.00    2.00    --   10.00 109.00  75.20   48
  9  \w    -35.00  -2.00   1.00    2.00    --   22.00 125.00 -99.48   33
 10  \w    -24.00   3.00   1.00    4.00    --   30.00 119.00  54.01   27
 11  \w     -1.00  26.00   1.00    4.00    --   38.00  94.00 125.85   27
 12  \w      5.00  33.00   1.00    4.00    --   42.00  89.00 128.56   28
 13  \w      6.00  33.00   1.00    4.00    --   42.00  88.00 -91.54   27
 14  \w     12.00  38.00   1.00    4.00    --   46.00  84.00-166.58   26
 15  \w     12.00  38.00   1.00    4.00    --   46.00  84.00  -0.45   26
 16  \w     14.00  46.00   1.00    4.00    --   46.00  81.00  51.53   32
 17  \w     13.00  40.00   1.00    4.00    --   46.00  83.00 -59.60   27
 18  \w     18.00  46.00   1.00    4.00    --   50.00  81.00-153.70   28
 19  \w     18.00  46.00   1.00    4.00    --   50.00  81.00  44.56   28
 20  \w     21.00 120.00   1.00    4.00    --   50.00  75.00 -52.46   99
 21  \w     17.00  45.00   1.00    4.00    --   50.00  82.00-103.60   28
 22  \w     17.00  45.00   1.00    4.00    --   50.00  82.00  89.74   28
 23  \w     18.00  46.00   1.00    4.00    --   50.00  80.00 151.92   28
 24  \w    -15.00  75.00   1.00    4.00    --   54.00 -57.00 150.00   90
 25  \w     23.00  49.00   1.00    4.00    --   54.00  78.00-162.79   26
 26  \w     23.00  49.00   1.00    4.00    --   54.00  78.00 146.41   26
 27  \w     24.00 124.00   1.00    4.00    --   54.00  77.00  22.21  100
 28  \w    -16.00  84.00   1.00    4.00    --   54.00 -77.00 -60.00  100
 29  \w     23.00 111.00   1.00    4.00    --   54.00-125.00  90.00   88
 30  \w     24.00 124.00   1.00    4.00    --   54.00  77.00-120.00  100
 31  \w     24.00 124.00   1.00    4.00    --   54.00  77.00  77.87  100
 32  \w     25.00 124.00   1.00    4.00    --   54.00  76.00  -6.64   99
 33  \w     24.00 124.00   1.00    4.00    --   54.00  77.00 -30.00  100
 34  \w     24.00 124.00   1.00    4.00    --   54.00  77.00  60.00  100
 35  \w     23.00 111.00   1.00    4.00    --   54.00-125.00 150.00   88
 36  \w     24.00 124.00   1.00    4.00    --   54.00  77.00 -90.00  100
 37  \w     24.00 124.00   1.00    4.00    --   54.00  77.00-150.00  100
 38  \w     24.00 124.00   1.00    4.00    --   54.00  77.00  90.00  100
 39  \w     24.00 124.00   1.00    4.00    --   54.00  77.00 -60.00  100
 40  \w     24.00 124.00   1.00    4.00    --   54.00  77.00-180.00  100
 41  \w     24.00 124.00   1.00    4.00    --   54.00  77.00 120.00  100
 42  \w     28.00 128.00   1.00    4.00    --   58.00  77.00  -7.62  100
 43  \w     28.00 128.00   1.00    4.00    --   58.00  77.00-103.77  100
 44  \w     28.00 128.00   1.00    4.00    --   58.00  77.00 -27.00  100
 45  \w     29.00 128.00   1.00    4.00    --   58.00  75.00 135.34   99
 46  \w     37.00 130.00   1.00    4.00    --   62.00  69.00-158.15   93
 47  \w     32.00 132.00   1.00    4.00    --   62.00  77.00  71.82  100
 48  \w     32.00 132.00   1.00    4.00    --   62.00  77.00 -48.54  100
 49  \w     36.00 131.00   1.00    4.00    --   62.00  70.00   1.12   95
 50  \w     32.00 132.00   1.00    4.00    --   62.00  77.00 151.92  100
 51  \w     32.00 132.00   1.00    4.00    --   62.00  77.00  20.04  100
 52  \w     37.00 136.00   1.00    4.00    --   66.00  76.00 117.22   99
 53  \w     36.00 136.00   1.00    4.00    --   66.00  77.00-116.09  100
 54  \w     37.00 136.00   1.00    4.00    --   66.00  76.00-147.60   99
 55  \w     45.00 135.00   1.00    4.00    --   66.00  57.00-163.60   90
 56  \w     38.00 136.00   1.00    4.00    --   66.00  74.00  15.15   98
 57  \w     36.00 136.00   1.00    4.00    --   66.00  77.00 -84.22  100
 58  \w     42.00 140.00   1.00    4.00    --   70.00  74.00  45.04   98
 59  \w     40.00 140.00   1.00    4.00    --   70.00  77.00-131.36  100
 60  \w     49.00 138.00   1.00    4.00    --   70.00  60.00 110.49   89
 61  \w     53.00 144.00   1.00    4.00    --   74.00  53.00-179.21   91
 62  \w     49.00 142.00   1.00    4.00    --   74.00  69.00-131.30   93
 63  \w     47.00 143.00   1.00    4.00    --   74.00  72.00 -77.49   96
 64  \w     51.00 141.00   1.00    4.00    --   74.00  64.00 135.68   90
 65  \w     46.00 144.00   1.00    4.00    --   74.00  74.00 -43.11   98
 66  \w     48.00 143.00   1.00    4.00    --   74.00  70.00  76.61   95
 67  \w     44.00 144.00   1.00    4.00    --   74.00  77.00  26.52  100
 68  \w     55.00 146.00   1.00    4.00    --   78.00  66.00 103.05   91
 69  \w     54.00 146.00   1.00    4.00    --   78.00  68.00  40.52   92
 70  \w     55.00 146.00   1.00    4.00    --   78.00  65.00-141.48   91
 71  \w     49.00 148.00   1.00    4.00    --   78.00  76.00  65.55   99
 72  \w     56.00 146.00   1.00    4.00    --   78.00  62.00  11.27   90
 73  \w     48.00 148.00   1.00    4.00    --   78.00  77.00 -20.60  100
 74  \w     49.00 148.00   1.00    4.00    --   78.00  75.00 174.67   99
 75  \w     57.00 147.00   1.00    4.00    --   78.00  55.00 -28.42   90
 76  \w     62.00 150.00   1.00    8.00    --   82.00  59.00 138.91   88
 77  \w     61.00 151.00   1.00    8.00    --   82.00  56.00-108.86   90
 78  \w     59.00 153.00   1.00    8.00    --   82.00  48.00 -46.68   94
 79  \w     58.00 150.00   1.00    8.00    --   82.00  67.00-166.69   92
 80  \w     59.00 155.00   1.00    8.00    --   86.00  72.00  81.35   96
 81  \w     59.00 155.00   1.00    8.00    --   86.00  71.00  88.36   96
 82  \w     57.00 156.00   1.00    8.00    --   86.00  76.00  42.75   99
 83  \w     60.00 155.00   1.00    8.00    --   86.00  70.00 -62.21   95
 84  \w     62.00 154.00   1.00    8.00    --   86.00  68.00-104.70   92
 85  \w     69.00 160.00   1.00    8.00    --   90.00  52.00 -33.94   91
 86  \w     71.00 161.00   1.00    8.00    --   94.00  64.00 -82.36   90
 87  \w     67.00 163.00   1.00    8.00    --   94.00  71.00 154.61   96
 88  \w     70.00 162.00   1.00    8.00    --   94.00  67.00  99.28   92
 89  \w     67.00 163.00   1.00    8.00    --   94.00  72.00-113.27   96
 90  \w     70.00 162.00   1.00    8.00    --   94.00  68.00 -36.38   92
 91  \w     67.00 163.00   1.00    8.00    --   94.00  72.00 -11.37   96
 92  \w     73.00 166.00   1.00    8.00    --   98.00  69.00-127.89   93
 93  \w     69.00 168.00   1.00    8.00    --   98.00  75.00 104.55   99
 94  \w     71.00 167.00   1.00    8.00    --   98.00  71.00  36.02   96
 95  \w     76.00 171.00   1.00    8.00    --  102.00  70.00  56.39   95
 96  \w     76.00 176.00   1.00    8.00    --  106.00  77.00  10.08  100
 97  \w     78.00 178.00   1.00    8.00    --  108.00  77.00  90.00  100
 98  \w     85.00 175.00   1.00    8.00    --  108.00  64.00 -90.00   90
 99  \w     78.00 178.00   1.00    8.00    --  108.00  77.00-150.00  100
100  \w     85.00 175.00   1.00    8.00    --  108.00  64.00 120.00   90
101  \w     78.00 178.00   1.00    8.00    --  108.00  77.00   0.00  100
102  \w     78.00 178.00   1.00    8.00    --  108.00  77.00 -30.00  100
103  \w    100.00 178.00   1.00    8.00    --  108.00 111.00   0.00   78
104  \w     78.00 178.00   1.00    8.00    --  108.00  77.00-180.00  100
105  \w     78.00 178.00   1.00    8.00    --  108.00  77.00 -60.00  100
106  \w     78.00 178.00   1.00    8.00    --  108.00  77.00  60.00  100
107  \w     78.00 178.00   1.00    8.00    --  108.00  77.00-120.00  100
108  \w     78.00 178.00   1.00    8.00    --  108.00  77.00 -90.00  100
109  \w     85.00 175.00   1.00    8.00    --  108.00  64.00   0.00   90
110  \w     78.00 178.00   1.00    8.00    --  108.00  77.00 150.00  100
111  \w     78.00 178.00   1.00    8.00    --  108.00  77.00  30.00  100
112  \w     85.00 175.00   1.00    8.00    --  108.00  64.00-150.00   90
113  \w     78.00 178.00   1.00    8.00    --  108.00  77.00 120.00  100
114  \w     36.00 116.00   1.00    8.00    --  108.00-111.00   0.00   80
115  \w     85.00 175.00   1.00    8.00    --  108.00  64.00-180.00   90
116  \w     41.00 131.00   1.00    8.00    --  108.00 -64.00  60.00   90
117  \w     85.00 175.00   1.00    8.00    --  108.00  64.00  90.00   90
118  \w     85.00 175.00   1.00    8.00    --  108.00  64.00 -30.00   90
119  \w     38.00 138.00   1.00    8.00    --  108.00 -77.00 -90.00  100
120  \w     36.00 116.00   1.00    8.00    --  108.00-111.00 150.00   80
121  \w     36.00 146.00   1.00    8.00    --  108.00 -92.00-150.00  110
122  \w     36.00 116.00   1.00    8.00    --  108.00-111.00  90.00   80
123  \w     81.00 177.00   1.00    8.00    --  108.00  72.00 138.35   96
124  \w     86.00 176.00   1.00    8.00    --  108.00  63.00 -66.17   90
125  \w     82.00 178.00   1.00    8.00    --  108.00  38.00-150.00   96
126  \w    100.00 178.00   1.00    8.00    --  108.00 111.00 -60.00   78
127  \w     82.00 178.00   1.00    8.00    --  108.00  38.00-120.00   96
128  \w     85.00 175.00   1.00    8.00    --  108.00  64.00 -60.00   90
129  \w     85.00 175.00   1.00    8.00    --  108.00  64.00-120.00   90
130  \f      0.00 120.00   1.00    2.00   0.00   0.00 -40.00    --   120
131  \f      0.00 120.00   1.00    2.00   0.00   0.00 -60.00    --   120
132  \f      0.00 120.00   1.00    2.00   0.00   0.00  60.00    --   120
133  \f      0.00 120.00   1.00    2.00   0.00   0.00  40.00    --   120
134  \f    120.00 240.00   1.00    2.00   0.00   0.00  40.00    --   120
135  \f    120.00 240.00   1.00    2.00   0.00   0.00 -60.00    --   120
136  \f    120.00 240.00   1.00    2.00   0.00   0.00  60.00    --   120
137  \f    240.00 360.00   1.00    2.00   0.00   0.00 -40.00    --   120
138  \f    240.00 360.00   1.00    2.00   0.00   0.00  40.00    --   120
139  \f    120.00 240.00   1.00    2.00   0.00   0.00 -40.00    --   120
140  \f      0.00 120.00   1.00    4.00  54.00  54.00 -40.00    --   120
;
_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      0.1273278000
_diffrn_orient_matrix_UB_12      0.0049544000
_diffrn_orient_matrix_UB_13      0.0282026000
_diffrn_orient_matrix_UB_21      0.0385958000
_diffrn_orient_matrix_UB_22      0.0777786000
_diffrn_orient_matrix_UB_23      -0.0219313000
_diffrn_orient_matrix_UB_31      -0.0405607000
_diffrn_orient_matrix_UB_32      0.0424831000
_diffrn_orient_matrix_UB_33      0.0576255000
_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  0.0298
_diffrn_reflns_av_unetI/netI     0.0120
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            243784
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.855
_diffrn_reflns_theta_min         3.423
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.439
_exptl_absorpt_correction_T_max  0.766
_exptl_absorpt_correction_T_min  0.555
_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    1.418
_exptl_crystal_description       block
_exptl_crystal_F_000             1952
_exptl_crystal_size_max          0.140
_exptl_crystal_size_mid          0.105
_exptl_crystal_size_min          0.064
_refine_diff_density_max         1.119
_refine_diff_density_min         -1.498
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.137
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1025
_refine_ls_number_reflns         17078
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.137
_refine_ls_R_factor_all          0.0267
_refine_ls_R_factor_gt           0.0261
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0071P)^2^+10.2137P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0565
_refine_ls_wR_factor_ref         0.0568
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16751
_reflns_number_total             17078
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00384_si_002.cif
_cod_data_source_block           ba_sb45
_cod_depositor_comments
'Adding full bibliography for 4086549--4086572.cif.'
_cod_database_code               4086571
_audit_block_refno               2628
_audit_block_usercomment         'sb462b, block, colourless'
_chemical_oxdiff_formula         'C49 H58 Hf N3 P Si2'
_chemical_oxdiff_usercomment     'sb462b, block, colourless'
_shelx_estimated_absorpt_t_max   0.612
_shelx_estimated_absorpt_t_min   0.612
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C1(H1A,H1B), C11(H11A,H11B), C28(H28A,H28B), C43(H43A,H43B), C51(H51A,H51B),
 C61(H61A,H61B), C78(H78A,H78B), C93(H93A,H93B)
2.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), C30(H30), C31(H31), C32(H32),
  C33(H33), C34(H34), C37(H37), C38(H38), C39(H39), C45(H45), C46(H46),
 C47(H47), C48(H48), C49(H49), 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), C80(H80), C81(H81), C82(H82), C83(H83), C84(H84), C87(H87), C88(H88),
  C89(H89), C95(H95), C96(H96), C97(H97), C98(H98), C99(H99)
2.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), C41(H41A,H41B,H41C), C42(H42A,H42B,
 H42C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C68(H68A,
 H68B,H68C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C91(H91A,H91B,H91C),
 C92(H92A,H92B,H92C)
;
_shelx_res_checksum              92699
_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 1.277
_oxdiff_exptl_absorpt_empirical_full_min 0.784
_cell_oxdiff_length_a            11.21305(9)
_cell_oxdiff_length_b            17.74642(13)
_cell_oxdiff_length_c            22.97468(19)
_cell_oxdiff_angle_alpha         98.1474(6)
_cell_oxdiff_angle_beta          91.2024(7)
_cell_oxdiff_angle_gamma         98.6327(6)
_cell_oxdiff_volume              4470.18(6)
_cell_oxdiff_measurement_reflns_used 159344