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_4086568
_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         'C50 H49 Hf N2 P'
_chemical_formula_sum            'C50 H49 Hf N2 P'
_chemical_formula_weight         887.37
_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_lm1
_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 14:17:46 CET UTC+01:00  encif 1.36'
_cell_angle_alpha                90
_cell_angle_beta                 99.948(8)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   24.105(13)
_cell_length_b                   17.206(9)
_cell_length_c                   22.372(11)
_cell_measurement_reflns_used    8173
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.84
_cell_measurement_theta_min      2.37
_cell_volume                     9139(8)
_computing_cell_refinement
;
SAINT (see _computing_data_reduction). Includes estimated systematic errors
 of the unit cell constants from Monte Carlo simulations.
;
_computing_data_collection       'SMART-5.631 (Bruker AXS, 2003)'
_computing_data_reduction
'SAINT (Bruker AXS, 1997-2013),SADABS-2014_5 (Sheldrick and Bruker AXS, 1997-2014)'
_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 polyether oil / N~2~'
_diffrn_ambient_temperature      100(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.19
_diffrn_detector_type            CCD-PXL-KAF2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker AXS Smart 1000'
_diffrn_measurement_method       '\f- and \w-scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0838
_diffrn_reflns_av_unetI/netI     0.0535
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            101635
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.176
_diffrn_reflns_theta_min         1.648
_diffrn_source                   'sealed X-Ray tube (Mo)'
_diffrn_source_type              'fine focus tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.351
_exptl_absorpt_correction_T_max  0.6478
_exptl_absorpt_correction_T_min  0.5692
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
multi-scan from symmetry-related measurements (Blessing 1995)
SADABS (see _computing_data_reduction)
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.290
_exptl_crystal_description       block
_exptl_crystal_F_000             3600
_exptl_crystal_size_max          0.170
_exptl_crystal_size_mid          0.160
_exptl_crystal_size_min          0.100
_refine_diff_density_max         2.661
_refine_diff_density_min         -2.409
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     592
_refine_ls_number_reflns         12334
_refine_ls_number_restraints     473
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.0658
_refine_ls_R_factor_gt           0.0410
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0340P)^2^+20.4075P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0800
_refine_ls_wR_factor_ref         0.0883
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9096
_reflns_number_total             12334
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00384_si_002.cif
_cod_data_source_block           ba_lm1_sq
_cod_depositor_comments
'Adding full bibliography for 4086549--4086572.cif.'
_cod_original_cell_volume        9140(8)
_cod_original_sg_symbol_H-M      'C 2/c'
_cod_database_code               4086568
_audit_block_refno               2583
_shelx_estimated_absorpt_t_max   0.799
_shelx_estimated_absorpt_t_min   0.691
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C25A-C29A \\sim C27A-C30A \\sim C25B-C29B \\sim C27B-C30B
 with sigma of 0.01
 N1-C8 \\sim N2-C23A \\sim N2-C23B
 with sigma of 0.005
 C37-C38A \\sim C37-C38B
 with sigma of 0.005
 C44-C45A \\sim C44-C45B
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23A \\sim C24A \\sim
C25A \\sim C26A \\sim C27A \\sim C28A \\sim C29A \\sim C30A \\sim C23B \\sim
C24B \\sim C25B \\sim C26B \\sim C27B \\sim C28B \\sim C29B \\sim C30B \\sim
C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38A
\\sim C39A \\sim C40A \\sim C41A \\sim C42A \\sim C43A \\sim C38B \\sim C39B
\\sim C40B \\sim C41B \\sim C42B \\sim C43B \\sim C44 \\sim C45A \\sim C46A
\\sim C47A \\sim C48A \\sim C49A \\sim C50A \\sim C45B \\sim C46B \\sim C47B
\\sim C48B \\sim C49B \\sim C50B: within 1A with sigma of 0.02 and sigma for
terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 N2, C23A, C24A, C25A, C26A, C27A, C28A, C29A, C30A, C23B, C24B, C25B, C26B,
 C27B, C28B, C29B, C30B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C44, C45A, C46A, C47A, C48A, C49A, C50A, C45B, C46B, C47B, C48B, C49B, C50B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C37, C38A, C39A, C40A, C41A, C42A, C43A, C38B, C39B, C40B, C41B, C42B, C43B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C23B)=Sof(C24B)=Sof(H24B)=Sof(C25B)=Sof(C26B)=Sof(H26B)=Sof(C27B)=
 Sof(C28B)=Sof(H28B)=Sof(C29B)=Sof(H29D)=Sof(H29E)=Sof(H29F)=Sof(C30B)=
 Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(1)
 Sof(C23A)=Sof(C24A)=Sof(H24A)=Sof(C25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=
 Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(H29A)=Sof(H29B)=Sof(H29C)=Sof(C30A)=
 Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(1)
 Sof(H44C)=Sof(H44D)=Sof(C45B)=Sof(C46B)=Sof(H46B)=Sof(C47B)=Sof(H47B)=
 Sof(C48B)=Sof(H48B)=Sof(C49B)=Sof(H49B)=Sof(C50B)=Sof(H50B)=1-FVAR(2)
 Sof(H44A)=Sof(H44B)=Sof(C45A)=Sof(C46A)=Sof(H46A)=Sof(C47A)=Sof(H47A)=
 Sof(C48A)=Sof(H48A)=Sof(C49A)=Sof(H49A)=Sof(C50A)=Sof(H50A)=FVAR(2)
 Sof(H37C)=Sof(H37D)=Sof(C38B)=Sof(C39B)=Sof(H39B)=Sof(C40B)=Sof(H40B)=
 Sof(C41B)=Sof(H41B)=Sof(C42B)=Sof(H42B)=Sof(C43B)=Sof(H43B)=1-FVAR(3)
 Sof(H37A)=Sof(H37B)=Sof(C38A)=Sof(C39A)=Sof(H39A)=Sof(C40A)=Sof(H40A)=
 Sof(C41A)=Sof(H41A)=Sof(C42A)=Sof(H42A)=Sof(C43A)=Sof(H43A)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C22(H22A,H22B), C37(H37A,H37B), C37(H37C,H37D), C44(H44A,H44B),
 C44(H44C,H44D)
6.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), C24A(H24A), C26A(H26A), C28A(H28A), C24B(H24B),
 C26B(H26B), C28B(H28B), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36),
 C39A(H39A), C40A(H40A), C41A(H41A), C42A(H42A), C43A(H43A), C39B(H39B),
 C40B(H40B), C41B(H41B), C42B(H42B), C43B(H43B), C46A(H46A), C47A(H47A),
 C48A(H48A), C49A(H49A), C50A(H50A), C46B(H46B), C47B(H47B), C48B(H48B),
 C49B(H49B), C50B(H50B)
6.c Fitted hexagon refined as free rotating group:
 C8(C9,C10,C11,C12,C13), C23A(C24A,C25A,C26A,C27A,C28A), C23B(C24B,C25B,C26B,
 C27B,C28B), C38A(C39A,C40A,C41A,C42A,C43A), C38B(C39B,C40B,C41B,C42B,C43B),
 C45A(C46A,C47A,C48A,C49A,C50A), C45B(C46B,C47B,C48B,C49B,C50B)
6.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C29A(H29A,H29B,H29C), C30A(H30A,
 H30B,H30C), C29B(H29D,H29E,H29F), C30B(H30D,H30E,H30F)
;
_shelx_res_checksum              14521
_olex2_submission_special_instructions 'No special instructions were received'
_platon_squeeze_void_probe_radius 1.20