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_4086561
_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 Hf I2 N2 P'
_chemical_formula_sum            'C38 H40 Hf I2 N2 O0.5 P'
_chemical_formula_weight         995.98
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      15
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ba_lm9
_audit_creation_date             2016-01-21
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
'21.01.2016 17:30:38 CET UTC+01:00  encif 1.38'
_cell_angle_alpha                90
_cell_angle_beta                 99.6396(9)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   22.0703(2)
_cell_length_b                   11.52011(9)
_cell_length_c                   29.7547(2)
_cell_measurement_reflns_used    53610
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      70.6150
_cell_measurement_theta_min      4.4860
_cell_volume                     7458.38(10)
_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 0.996
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

--------------------------------------------------------------------------
  1  \w    -72.00  26.00   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 -60.00  100
  3  \w    -52.00   5.00   1.00    2.00    --    0.00 117.00  45.00   57
  4  \w    -60.00  38.00   1.00    2.00    --   10.00 -74.00-177.97   98
  5  \w    -42.00   0.00   1.00    2.00    --   14.00 123.00-169.67   42
  6  \w    -23.00   9.00   1.00    2.00    --   26.00 112.00  90.51   32
  7  \w     -9.00  18.00   1.00    8.00    --   34.00 102.00 -94.34   27
  8  \w      6.00  33.00   1.00    8.00    --   42.00  88.00  -1.87   27
  9  \w      5.00  32.00   1.00    8.00    --   42.00  90.00-107.09   27
 10  \w     12.00  38.00   1.00    8.00    --   46.00  84.00  59.81   26
 11  \w     12.00  38.00   1.00    8.00    --   46.00  84.00 141.08   26
 12  \w     12.00  38.00   1.00    8.00    --   46.00  84.00 -85.51   26
 13  \w     18.00  46.00   1.00    8.00    --   50.00  81.00  87.83   28
 14  \w     18.00  46.00   1.00    8.00    --   50.00  81.00  38.57   28
 15  \w     17.00  45.00   1.00    8.00    --   50.00  82.00-128.35   28
 16  \w     19.00  47.00   1.00    8.00    --   50.00  79.00-172.19   28
 17  \w     18.00  46.00   1.00    8.00    --   50.00  80.00 140.54   28
 18  \w     18.00  46.00   1.00    8.00    --   50.00  81.00 -17.28   28
 19  \w     23.00 111.00   1.00    8.00    --   54.00-125.00   0.00   88
 20  \w    -16.00  84.00   1.00    8.00    --   54.00 -77.00 120.00  100
 21  \w     23.00  49.00   1.00    8.00    --   54.00  78.00  19.97   26
 22  \w      1.00  96.00   1.00    8.00    --   54.00 -99.00-150.00   95
 23  \w    -15.00  75.00   1.00    8.00    --   54.00 -57.00   0.00   90
 24  \w     28.00 128.00   1.00    8.00    --   58.00  77.00  84.63  100
 25  \w     31.00 127.00   1.00    8.00    --   58.00  71.00-175.30   96
 26  \w     29.00 128.00   1.00    8.00    --   58.00  76.00 120.99   99
 27  \w     28.00 128.00   1.00    8.00    --   58.00  77.00 -60.03  100
 28  \w     34.00 131.00   1.00    8.00    --   62.00  73.00-148.60   97
 29  \w     33.00 132.00   1.00    8.00    --   62.00  75.00 -94.45   99
 30  \w     32.00 132.00   1.00    8.00    --   62.00  77.00 -44.44  100
 31  \w     36.00 136.00   1.00    8.00    --   66.00  77.00  41.51  100
 32  \w     36.00 136.00   1.00    8.00    --   66.00  77.00-123.39  100
 33  \w     45.00 138.00   1.00    8.00    --   70.00  69.00 -19.22   93
 34  \w     42.00 139.00   1.00    8.00    --   70.00  73.00 170.83   97
 35  \w     40.00 140.00   1.00    8.00    --   70.00  77.00 127.04  100
 36  \w     51.00 142.00   1.00    8.00    --   74.00  65.00 -94.82   91
 37  \w     46.00 144.00   1.00    8.00    --   74.00  74.00  10.45   98
 38  \w     52.00 142.00   1.00    8.00    --   74.00  63.00  85.98   90
 39  \w     53.00 146.00   1.00    8.00    --   78.00  69.00-177.57   93
 40  \w     49.00 148.00   1.00    8.00    --   78.00  76.00 -76.06   99
 41  \w     52.00 147.00   1.00    8.00    --   78.00  70.00 162.33   95
 42  \w     51.00 147.00   1.00    8.00    --   78.00  72.00-161.71   96
 43  \w     51.00 147.00   1.00    8.00    --   78.00  71.00 -22.35   96
 44  \w     52.00 147.00   1.00    8.00    --   78.00  70.00  38.32   95
 45  \w     48.00 148.00   1.00    8.00    --   78.00  77.00  88.54  100
 46  \w     53.00 152.00   1.00   16.00    --   82.00  75.00-141.85   99
 47  \w     55.00 151.00   1.00   16.00    --   82.00  71.00 136.63   96
 48  \w     59.00 155.00   1.00   16.00    --   86.00  72.00  84.46   96
 49  \w     65.00 155.00   1.00   16.00    --   86.00  55.00  12.17   90
 50  \w     56.00 156.00   1.00   16.00    --   86.00  77.00 -71.45  100
 51  \w     57.00 156.00   1.00   16.00    --   86.00  75.00 104.04   99
 52  \w     65.00 158.00   1.00   16.00    --   90.00  69.00 -62.67   93
 53  \w     61.00 160.00   1.00   16.00    --   90.00  75.00 -89.95   99
 54  \w     70.00 162.00   1.00   16.00    --   94.00  68.00 140.72   92
 55  \w     68.00 163.00   1.00   16.00    --   94.00  70.00  15.68   95
 56  \w     68.00 163.00   1.00   16.00    --   94.00  70.00-119.08   95
 57  \w     76.00 166.00   1.00   16.00    --   98.00  62.00 176.84   90
 58  \w     77.00 168.00   1.00   16.00    --   98.00  53.00 172.85   91
 59  \w     78.00 143.00   1.00   16.00    --  106.00  74.00  79.34   65
 60  \w     41.00 131.00   1.00   16.00    --  108.00 -64.00  30.00   90
 61  \w     78.00 174.00   1.00   16.00    --  108.00  77.00 -60.00   96
 62  \w     43.00 129.00   1.00   16.00    --  108.00 -64.00-150.00   86
 63  \w     47.00 118.00   1.00   16.00    --  108.00 -92.00   0.00   71
 64  \w     50.00  81.00   1.00   16.00    --  108.00-111.00-150.00   31
 65  \w     78.00 115.00   1.00   16.00    --  108.00  77.00-171.47   37
 66  \w     78.00 104.00   1.00   16.00    --  108.00  77.00  22.57   26
 67  \w     85.00 110.00   1.00   16.00    --  108.00  64.00 -30.00   25
 68  \w     78.00 166.00   1.00   16.00    --  108.00  77.00-120.00   88
 69  \w     78.00 174.00   1.00   16.00    --  108.00  77.00 120.00   96
 70  \w     52.00 109.00   1.00   16.00    --  108.00-111.00-120.00   57
 71  \w     78.00 171.00   1.00   16.00    --  108.00  77.00  60.00   93
 72  \w     78.00 164.00   1.00   16.00    --  108.00  77.00  30.00   86
 73  \w     78.00 165.00   1.00   16.00    --  108.00  77.00   0.00   87
 74  \w    115.00 167.00   1.00   16.00    --  108.00  77.00-180.00   52
 75  \w     78.00 104.00   1.00   16.00    --  108.00  77.00-180.00   26
 76  \w     78.00 162.00   1.00   16.00    --  108.00  77.00 -90.00   84
 77  \w     78.00 166.00   1.00   16.00    --  108.00  77.00  90.00   88
 78  \w     78.00 170.00   1.00   16.00    --  108.00  77.00 -30.00   92
 79  \w     73.00 110.00   1.00   16.00    --  108.00-111.00 150.00   37
 80  \w     78.00 169.00   1.00   16.00    --  108.00  77.00-150.00   91
 81  \w     78.00 178.00   1.00   16.00    --  108.00  77.00 150.00  100
 82  \w     73.00 116.00   1.00   16.00    --  108.00-111.00 -30.00   43
;
_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      0.0032722000
_diffrn_orient_matrix_UB_12      -0.0109007000
_diffrn_orient_matrix_UB_13      0.0519558000
_diffrn_orient_matrix_UB_21      -0.0282877000
_diffrn_orient_matrix_UB_22      0.1220019000
_diffrn_orient_matrix_UB_23      0.0012436000
_diffrn_orient_matrix_UB_31      -0.0648073000
_diffrn_orient_matrix_UB_32      -0.0537635000
_diffrn_orient_matrix_UB_33      -0.0075406000
_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  0.0355
_diffrn_reflns_av_unetI/netI     0.0134
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            105872
_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         70.776
_diffrn_reflns_theta_min         4.063
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    18.795
_exptl_absorpt_correction_T_max  0.08853
_exptl_absorpt_correction_T_min  0.01512
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41p (Rigaku Oxford Diffraction, 2015)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
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    1.774
_exptl_crystal_description       irregular
_exptl_crystal_F_000             3832
_exptl_crystal_size_max          0.250
_exptl_crystal_size_mid          0.095
_exptl_crystal_size_min          0.040
_refine_diff_density_max         2.165
_refine_diff_density_min         -0.367
_refine_diff_density_rms         0.217
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.293
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     383
_refine_ls_number_reflns         7144
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.293
_refine_ls_R_factor_all          0.0454
_refine_ls_R_factor_gt           0.0446
_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^)+(0.0673P)^2^+5.6467P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1093
_refine_ls_wR_factor_ref         0.1101
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6926
_reflns_number_total             7144
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00384_si_002.cif
_cod_data_source_block           ba_lm9_sq
_cod_depositor_comments
'Adding full bibliography for 4086549--4086572.cif.'
_cod_original_cell_volume        7458.36(11)
_cod_original_sg_symbol_H-M      'C 2/c'
_cod_original_formula_sum        'C38 H40 Hf I2 N2 O0.50 P'
_cod_database_code               4086561
_audit_block_refno               2629
_audit_block_usercomment         'lm117, irregular, yellow'
_chemical_oxdiff_formula         'C36 H35 Hf I2 N2 P (O1 C4 H10)0.5'
_chemical_oxdiff_usercomment     'lm117, irregular, yellow'
_shelx_estimated_absorpt_t_max   0.255
_shelx_estimated_absorpt_t_min   0.255
_reflns_odcompleteness_completeness 99.97
_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:
 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)
;
_shelx_res_checksum              89576
_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 1.928
_oxdiff_exptl_absorpt_empirical_full_min 0.728
_cell_oxdiff_length_a            22.0759(4)
_cell_oxdiff_length_b            11.51670(17)
_cell_oxdiff_length_c            29.7573(4)
_cell_oxdiff_angle_alpha         89.9263(11)
_cell_oxdiff_angle_beta          99.6558(12)
_cell_oxdiff_angle_gamma         89.9971(12)
_cell_oxdiff_volume              7458.36(19)
_cell_oxdiff_measurement_reflns_used 53610
_platon_squeeze_void_probe_radius 1.20