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_4086565
_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 H49 Hf N2 P Si2'
_chemical_formula_sum            'C40 H49 Hf N2 P Si2'
_chemical_formula_weight         823.45
_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/c 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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ba_sb41
_audit_creation_date             2015-12-04
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
'04.12.2015 10:39:09 CET UTC+01:00  encif 1.36'
_cell_angle_alpha                90
_cell_angle_beta                 117.9006(19)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.25124(15)
_cell_length_b                   39.7877(5)
_cell_length_c                   10.27791(15)
_cell_measurement_reflns_used    49839
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      70.9620
_cell_measurement_theta_min      4.4510
_cell_volume                     3704.80(11)
_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 1.000
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

--------------------------------------------------------------------------
  1  \w    -17.00  10.00   1.00    5.00    --    0.00  38.00 120.00   27
  2  \w    -72.00 -36.00   1.00    5.00    --    0.00 -38.00  90.00   36
  3  \w    -19.00  24.00   1.00    5.00    --    0.00  38.00-150.00   43
  4  \w     -8.00  25.00   1.00    5.00    --    0.00 -38.00  90.00   33
  5  \w     -4.00  65.00   1.00    5.00    --    0.00  57.00 -90.00   69
  6  \w     12.00  71.00   1.00    5.00    --    0.00  38.00 120.00   59
  7  \w     26.00  70.00   1.00    5.00    --    0.00  38.00-150.00   44
  8  \w    -33.00  -8.00   1.00    5.00    --   14.00 110.00  15.71   25
  9  \w    -32.00   0.00   1.00    5.00    --   18.00 115.00-162.43   32
 10  \w    -21.00   4.00   1.00   10.00    --   30.00 115.00 152.74   25
 11  \w    -10.00  15.00   1.00   10.00    --   34.00 104.00  33.89   25
 12  \w      6.00  31.00   1.00   10.00    --   42.00  88.00  87.65   25
 13  \w      6.00  31.00   1.00   10.00    --   42.00  88.00 -30.02   25
 14  \w     12.00  37.00   1.00   10.00    --   46.00  84.00 176.93   25
 15  \w     13.00  38.00   1.00   10.00    --   46.00  83.00-123.49   25
 16  \w     13.00  38.00   1.00   10.00    --   46.00  83.00  57.82   25
 17  \w     13.00  38.00   1.00   10.00    --   46.00  82.00   5.94   25
 18  \w     12.00  37.00   1.00   10.00    --   46.00  84.00  98.15   25
 19  \w     12.00  37.00   1.00   10.00    --   46.00  84.00 167.54   25
 20  \w     18.00  43.00   1.00   10.00    --   50.00  80.00-123.63   25
 21  \w     17.00  42.00   1.00   10.00    --   50.00  82.00 -43.38   25
 22  \w     19.00  44.00   1.00   10.00    --   50.00  79.00 129.45   25
 23  \w     21.00  47.00   1.00   10.00    --   50.00  76.00 -80.78   26
 24  \w     19.00  44.00   1.00   10.00    --   50.00  79.00-158.68   25
 25  \w     19.00  44.00   1.00   10.00    --   50.00  79.00  93.49   25
 26  \w     17.00  42.00   1.00   10.00    --   50.00  82.00  53.32   25
 27  \w     24.00  50.00   1.00   10.00    --   54.00  77.00-159.17   26
 28  \w     23.00  48.00   1.00   10.00    --   54.00  78.00 -82.59   25
 29  \w     -5.00  84.00   1.00   10.00    --   54.00 -77.00 -30.00   89
 30  \w     25.00  51.00   1.00   10.00    --   54.00  77.00 150.00   26
 31  \w     24.00  50.00   1.00   10.00    --   54.00  77.00 -90.00   26
 32  \w     23.00  48.00   1.00   10.00    --   54.00  78.00  18.28   25
 33  \w     26.00  52.00   1.00   10.00    --   54.00  77.00-120.00   26
 34  \w     27.00  53.00   1.00   10.00    --   54.00  77.00   0.00   26
 35  \w     32.00  58.00   1.00   10.00    --   54.00  77.00  90.00   26
 36  \w    -14.00  75.00   1.00   10.00    --   54.00 -57.00-120.00   89
 37  \w     23.00 106.00   1.00   10.00    --   54.00-125.00-180.00   83
 38  \w     27.00  53.00   1.00   10.00    --   54.00  77.00  60.00   26
 39  \w     28.00  54.00   1.00   10.00    --   54.00  77.00 -30.00   26
 40  \w     26.00  52.00   1.00   10.00    --   54.00  77.00-180.00   26
 41  \w     29.00  55.00   1.00   10.00    --   54.00  77.00 120.00   26
 42  \w     24.00  66.00   1.00   10.00    --   54.00-125.00-120.00   42
 43  \w     29.00  55.00   1.00   10.00    --   58.00  76.00  62.71   26
 44  \w     39.00 110.00   1.00   10.00    --   58.00  65.00  35.41   71
 45  \w     28.00  54.00   1.00   10.00    --   58.00  77.00 178.51   26
 46  \w     29.00  55.00   1.00   10.00    --   58.00  75.00 137.33   26
 47  \w     93.00 123.00   1.00   10.00    --   58.00  77.00 -67.14   30
 48  \w     28.00  53.00   1.00   10.00    --   58.00  77.00 -67.14   25
 49  \w     30.00  59.00   1.00   10.00    --   58.00  75.00 -43.36   29
 50  \w     34.00  60.00   1.00   10.00    --   58.00  72.00 -96.40   26
 51  \w     34.00  60.00   1.00   10.00    --   62.00  74.00 120.94   26
 52  \w     35.00  61.00   1.00   10.00    --   62.00  72.00 -93.07   26
 53  \w     40.00  66.00   1.00   10.00    --   62.00  74.00 142.34   26
 54  \w    101.00 128.00   1.00   10.00    --   62.00  75.00  -7.53   27
 55  \w     68.00  94.00   1.00   10.00    --   62.00  75.00  -7.53   26
 56  \w     45.00  97.00   1.00   10.00    --   62.00  68.00  74.23   52
 57  \w     40.00  75.00   1.00   10.00    --   62.00  62.00-150.45   35
 58  \w     34.00  59.00   1.00   10.00    --   62.00  75.00  -7.53   25
 59  \w     35.00  61.00   1.00   10.00    --   62.00  76.00 -64.21   26
 60  \w     38.00  64.00   1.00   10.00    --   66.00  76.00  27.78   26
 61  \w     40.00  66.00   1.00   10.00    --   66.00  70.00-155.95   26
 62  \w     45.00  83.00   1.00   10.00    --   66.00  49.00  14.64   38
 63  \w     46.00 134.00   1.00   10.00    --   66.00  58.00-102.35   88
 64  \w     40.00  65.00   1.00   10.00    --   66.00  70.00 169.21   25
 65  \w     46.00  72.00   1.00   10.00    --   70.00  69.00-161.36   26
 66  \w     49.00  85.00   1.00   10.00    --   70.00  55.00 170.40   36
 67  \w     43.00 100.00   1.00   10.00    --   70.00  74.00 113.47   57
 68  \w     43.00  69.00   1.00   10.00    --   70.00  76.00  41.80   26
 69  \w     53.00  84.00   1.00   10.00    --   74.00  68.00  41.29   31
 70  \w     49.00  75.00   1.00   10.00    --   74.00  69.00-101.46   26
 71  \w     48.00  75.00   1.00   10.00    --   74.00  73.00  80.65   27
 72  \w     48.00 122.00   1.00   10.00    --   74.00  71.00-149.94   74
 73  \w     44.00  70.00   1.00   10.00    --   74.00  77.00 -16.22   26
 74  \w     51.00  77.00   1.00   10.00    --   74.00  66.00 -54.36   26
 75  \w     57.00 122.00   1.00   10.00    --   78.00  57.00-165.69   65
 76  \w     49.00  75.00   1.00   10.00    --   78.00  77.00 -13.85   26
 77  \w     51.00  76.00   1.00   10.00    --   78.00  72.00  69.26   25
 78  \w     57.00  82.00   1.00   10.00    --   78.00  50.00 158.02   25
 79  \w     55.00  87.00   1.00   10.00    --   78.00  65.00 -78.74   32
 80  \w     51.00 147.00   1.00   10.00    --   78.00  71.00 -54.63   96
 81  \w     59.00  85.00   1.00   15.00    --   82.00  74.00 -12.14   26
 82  \w     61.00 114.00   1.00   15.00    --   82.00  60.00  44.59   53
 83  \w     54.00  80.00   1.00   15.00    --   82.00  73.00 145.51   26
 84  \w     59.00 111.00   1.00   15.00    --   86.00  72.00  71.44   52
 85  \w     59.00  85.00   1.00   15.00    --   86.00  71.00-177.52   26
 86  \w     63.00  89.00   1.00   15.00    --   86.00  48.00   7.49   26
 87  \w    120.00 147.00   1.00   15.00    --   86.00  60.00 171.73   27
 88  \w     65.00 114.00   1.00   15.00    --   86.00  60.00 171.73   49
 89  \w     66.00 135.00   1.00   15.00    --   90.00  68.00  13.12   69
 90  \w     63.00 159.00   1.00   15.00    --   90.00  72.00-144.75   96
 91  \w     60.00  90.00   1.00   15.00    --   90.00  77.00 -62.15   30
 92  \w     77.00 126.00   1.00   15.00    --   90.00  70.00-167.14   49
 93  \w     68.00 104.00   1.00   15.00    --   90.00  61.00   1.48   36
 94  \w     60.00  86.00   1.00   15.00    --   90.00  77.00 179.32   26
 95  \w     67.00 104.00   1.00   15.00    --   94.00  71.00 120.40   37
 96  \w     73.00  99.00   1.00   15.00    --   94.00  65.00 136.92   26
 97  \w     68.00  98.00   1.00   15.00    --   98.00  77.00-110.34   30
 98  \w     78.00 113.00   1.00   15.00    --  102.00  44.00 -32.38   35
 99  \w     85.00 174.00   1.00   15.00    --  108.00  64.00 -30.00   89
100  \w     79.00 105.00   1.00   15.00    --  108.00  77.00-180.00   26
101  \w     41.00 130.00   1.00   15.00    --  108.00 -64.00 150.00   89
102  \w     85.00 111.00   1.00   15.00    --  108.00  64.00  90.00   26
103  \w     46.00 112.00   1.00   15.00    --  108.00-111.00  90.00   66
104  \w     83.00 109.00   1.00   15.00    --  108.00  77.00-120.00   26
105  \w     86.00 165.00   1.00   15.00    --  108.00  64.00  30.00   79
106  \w     80.00 106.00   1.00   15.00    --  108.00  77.00 150.00   26
107  \w     79.00 105.00   1.00   15.00    --  108.00  77.00 120.00   26
108  \w     78.00 103.00   1.00   15.00    --  108.00  77.00  60.00   25
109  \w    109.00 135.00   1.00   15.00    --  108.00  77.00  90.00   26
110  \w     78.00 103.00   1.00   15.00    --  108.00  77.00  90.00   25
111  \w    116.00 177.00   1.00   15.00    --  108.00  77.00-150.00   61
112  \w     78.00 104.00   1.00   15.00    --  108.00  77.00-150.00   26
113  \w     86.00 175.00   1.00   15.00    --  108.00  64.00-180.00   89
114  \w    100.00 138.00   1.00   15.00    --  108.00 -77.00   0.00   38
115  \w     39.00  93.00   1.00   15.00    --  108.00 -77.00   0.00   54
116  \w     78.00 178.00   1.00   15.00    --  108.00  77.00 -90.00  100
117  \w     78.00 104.00   1.00   15.00    --  108.00  77.00 -30.00   26
118  \w     79.00 105.00   1.00   15.00    --  108.00  77.00 -60.00   26
119  \w     43.00 113.00   1.00   15.00    --  108.00 -38.00 -90.00   70
120  \w    133.00 165.00   1.00   15.00    --  108.00  38.00 -90.00   32
121  \w     82.00 128.00   1.00   15.00    --  108.00  38.00 -90.00   46
122  \w     85.00 174.00   1.00   15.00    --  108.00  64.00 120.00   89
123  \w     73.00 107.00   1.00   15.00    --  108.00-111.00-120.00   34
124  \w     78.00 103.00   1.00   15.00    --  108.00  77.00  30.00   25
125  \w     83.00 156.00   1.00   15.00    --  108.00  38.00 120.00   73
126  \w     86.00 112.00   1.00   15.00    --  108.00  64.00 150.00   26
127  \w     87.00 175.00   1.00   15.00    --  108.00  64.00  60.00   88
128  \w    117.00 146.00   1.00   15.00    --  108.00 -92.00-120.00   29
129  \w     64.00  90.00   1.00   15.00    --  108.00 -92.00-120.00   26
130  \w    100.00 140.00   1.00   15.00    --  108.00 -92.00  60.00   40
131  \w     36.00 115.00   1.00   15.00    --  108.00-111.00 -30.00   79
132  \w     91.00 117.00   1.00   15.00    --  108.00  70.00   9.41   26
133  \w    151.00 177.00   1.00   15.00    --  108.00  74.00  -4.39   26
134  \w     86.00 127.00   1.00   15.00    --  108.00  38.00-180.00   41
135  \w     81.00 107.00   1.00   15.00    --  108.00  74.00  -4.39   26
136  \w     84.00 178.00   1.00   15.00    --  108.00  38.00   0.00   94
137  \w     85.00 111.00   1.00   15.00    --  108.00  64.00   0.00   26
138  \w    125.00 174.00   1.00   15.00    --  108.00  64.00 -60.00   49
139  \w     85.00 112.00   1.00   15.00    --  108.00  64.00 -60.00   27
140  \w    130.00 158.00   1.00   15.00    --  108.00  38.00-180.00   28
141  \w     85.00 116.00   1.00   15.00    --  108.00  38.00-120.00   31
142  \w     85.00 111.00   1.00   15.00    --  108.00  38.00  30.00   26
143  \w     85.00 138.00   1.00   15.00    --  108.00  64.00 -90.00   53
144  \w    142.00 174.00   1.00   15.00    --  108.00  64.00-120.00   32
145  \w     85.00 111.00   1.00   15.00    --  108.00  64.00-120.00   26
146  \w     79.00 105.00   1.00   15.00    --  108.00  77.00   0.00   26
147  \w     86.00 112.00   1.00   15.00    --  108.00  64.00-150.00   26
148  \f   -150.00 120.00   1.00    0.50   0.00   0.00   0.00    --   270
;
_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      0.0921228000
_diffrn_orient_matrix_UB_12      -0.0068899000
_diffrn_orient_matrix_UB_13      0.1661205000
_diffrn_orient_matrix_UB_21      0.1316237000
_diffrn_orient_matrix_UB_22      -0.0106582000
_diffrn_orient_matrix_UB_23      -0.0240534000
_diffrn_orient_matrix_UB_31      0.0557196000
_diffrn_orient_matrix_UB_32      0.0365774000
_diffrn_orient_matrix_UB_33      0.0242701000
_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  0.0311
_diffrn_reflns_av_unetI/netI     0.0126
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       48
_diffrn_reflns_limit_k_min       -44
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            94255
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.832
_diffrn_reflns_theta_min         4.445
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.456
_exptl_absorpt_correction_T_max  0.757
_exptl_absorpt_correction_T_min  0.579
_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            'light colourless'
_exptl_crystal_density_diffrn    1.476
_exptl_crystal_description       plate
_exptl_crystal_F_000             1672
_exptl_crystal_size_max          0.096
_exptl_crystal_size_mid          0.063
_exptl_crystal_size_min          0.054
_refine_diff_density_max         0.545
_refine_diff_density_min         -1.102
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.315
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     433
_refine_ls_number_reflns         7106
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.315
_refine_ls_R_factor_all          0.0265
_refine_ls_R_factor_gt           0.0258
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+5.9035P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0487
_refine_ls_wR_factor_ref         0.0489
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6989
_reflns_number_total             7106
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00384_si_002.cif
_cod_data_source_block           ba_sb41
_cod_depositor_comments
'Adding full bibliography for 4086549--4086572.cif.'
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               4086565
_audit_block_refno               2592
_audit_block_usercomment         'sb417b, plate, colourless'
_chemical_oxdiff_formula         'C40 H49 N2 P Si2 Hf'
_chemical_oxdiff_usercomment     'sb417b, plate, colourless'
_shelx_estimated_absorpt_t_max   0.565
_shelx_estimated_absorpt_t_min   0.565
_reflns_odcompleteness_completeness 99.96
_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)
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), C29(H29), C30(H30), C31(H31),
  C32(H32), C33(H33), C36(H36), C37(H37), C38(H38), C39(H39), C40(H40)
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)
;
_shelx_res_checksum              4364
_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 1.279
_oxdiff_exptl_absorpt_empirical_full_min 0.834
_cell_oxdiff_length_a            10.25005(15)
_cell_oxdiff_length_b            39.7907(5)
_cell_oxdiff_length_c            10.27717(16)
_cell_oxdiff_angle_alpha         89.9933(11)
_cell_oxdiff_angle_beta          117.8884(16)
_cell_oxdiff_angle_gamma         90.0069(11)
_cell_oxdiff_volume              3704.80(9)
_cell_oxdiff_measurement_reflns_used 49839