Robust Chromium Precursors for Catalysis: Isolation and Structure of a Single-Component Ethylene Tetramerization Precatalyst.
Hirscher, Nathanael A.; Perez Sierra, Danny; Agapie, Theodor; Journal of the American Chemical Society 141 (2019) 6022–6029; doi:10.1021/jacs.9b01387

data_4128434
_publ_section_title
;
 Robust Chromium Precursors for Catalysis: Isolation and Structure of a
 Single-Component Ethylene Tetramerization Precatalyst.
;
_journal_issue                   14
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6022
_journal_page_last               6029
_journal_paper_doi               10.1021/jacs.9b01387
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety
'C45 H49 Cr N O2 P2, C0.5 H Cl, C32 H12 B F24'
_chemical_formula_sum            'C77.5 H62 B Cl Cr F24 N O2 P2'
_chemical_formula_weight         1655.48
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-01-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                104.445(2)
_cell_angle_beta                 96.510(2)
_cell_angle_gamma                107.746(2)
_cell_formula_units_Z            2
_cell_length_a                   12.9268(7)
_cell_length_b                   16.7595(10)
_cell_length_c                   18.9950(9)
_cell_measurement_reflns_used    9651
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      33.65
_cell_measurement_theta_min      2.57
_cell_volume                     3714.6(4)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.01
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0508
_diffrn_reflns_av_unetI/netI     0.0379
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            199425
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.748
_diffrn_reflns_theta_min         2.263
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.341
_exptl_absorpt_correction_T_max  0.7467
_exptl_absorpt_correction_T_min  0.7161
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0813 before and 0.0577 after correction. The Ratio of minimum to maximum transmission is 0.9590. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.480
_exptl_crystal_description       plate
_exptl_crystal_F_000             1684
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.197
_refine_diff_density_min         -2.170
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.100
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1135
_refine_ls_number_reflns         29673
_refine_ls_number_restraints     369
_refine_ls_restrained_S_all      1.135
_refine_ls_R_factor_all          0.0808
_refine_ls_R_factor_gt           0.0621
_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^)+(0.0590P)^2^+3.2570P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1413
_refine_ls_wR_factor_ref         0.1500
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23749
_reflns_number_total             29673
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b01387_si_001.cif
_cod_data_source_block           v18368_a
_cod_original_formula_sum        'C77.50 H62 B Cl Cr F24 N O2 P2'
_cod_database_code               4128434
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.967
_shelx_estimated_absorpt_t_min   0.935
_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. Restrained distances
 F1A-C66 \\sim F2A-C66 \\sim F3A-C66 \\sim F4A-C66 \\sim F5A-C66 \\sim F6A-C66
 with sigma of 0.02
 C63-F3A \\sim C63-F4A \\sim C63-F5A \\sim C63-F6A \\sim C63-F1A \\sim C63-F2A
 with sigma of 0.02
 F4A-F6A \\sim F4A-F2A \\sim F6A-F2A \\sim F3A-F5A \\sim F1A-F3A \\sim F5A-F1A
 with sigma of 0.02
 F1B-C57 \\sim F2B-C57 \\sim F3B-C57 \\sim F4B-C57 \\sim F5B-C57 \\sim F6B-C57
 with sigma of 0.02
 C53-F3B \\sim C53-F4B \\sim C53-F5B \\sim C53-F6B \\sim C53-F1B \\sim C53-F2B
 with sigma of 0.02
 F4B-F6B \\sim F4B-F2B \\sim F6B-F2B \\sim F3B-F5B \\sim F1B-F3B \\sim F5B-F1B
 with sigma of 0.02
 F1C-C58 \\sim F2C-C58 \\sim F3C-C58 \\sim F4C-C58 \\sim F5C-C58 \\sim F6C-C58
 with sigma of 0.02
 C55-F3C \\sim C55-F4C \\sim C55-F5C \\sim C55-F6C \\sim C55-F1C \\sim C55-F2C
 with sigma of 0.02
 F4C-F6C \\sim F4C-F2C \\sim F6C-F2C \\sim F3C-F5C \\sim F1C-F3C \\sim F5C-F1C
 with sigma of 0.02
 F1D-C50 \\sim F2D-C50 \\sim F3D-C50 \\sim F4D-C50 \\sim F5D-C50 \\sim F6D-C50
 with sigma of 0.02
 C47-F3D \\sim C47-F4D \\sim C47-F5D \\sim C47-F6D \\sim C47-F1D \\sim C47-F2D
 with sigma of 0.02
 F4D-F6D \\sim F4D-F2D \\sim F6D-F2D \\sim F3D-F5D \\sim F1D-F3D \\sim F5D-F1D
 with sigma of 0.02
 F1E-C49 \\sim F2E-C49 \\sim F3E-C49 \\sim F4E-C49 \\sim F5E-C49 \\sim F6E-C49
 with sigma of 0.02
 C45-F3E \\sim C45-F4E \\sim C45-F5E \\sim C45-F6E \\sim C45-F1E \\sim C45-F2E
 with sigma of 0.02
 F4E-F6E \\sim F4E-F2E \\sim F6E-F2E \\sim F3E-F5E \\sim F1E-F3E \\sim F5E-F1E
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 F6A, F5A, F1A, F2A, F4A, F3A, C66
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F6B, F1B, F2B, F3B, F4B, F5B, C57
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F5D, F6D, F1D, F2D, F3D, F4D, C50
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1C, F2C, F3C, F4C, F5C, F6C, C58
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(F4A)=Sof(F6A)=Sof(F2A)=1-FVAR(1)
 Sof(F1A)=Sof(F3A)=Sof(F5A)=FVAR(1)
 Sof(F3B)=Sof(F1B)=Sof(F5B)=1-FVAR(2)
 Sof(F4B)=Sof(F6B)=Sof(F2B)=FVAR(2)
 Sof(F6C)=Sof(F2C)=Sof(F4C)=1-FVAR(3)
 Sof(F3C)=Sof(F5C)=Sof(F1C)=FVAR(3)
 Sof(F6D)=Sof(F2D)=Sof(F4D)=1-FVAR(4)
 Sof(F3D)=Sof(F5D)=Sof(F1D)=FVAR(4)
 Sof(F2E)=Sof(F6E)=Sof(F4E)=1-FVAR(5)
 Sof(F5E)=Sof(F1E)=Sof(F3E)=FVAR(5)
 Fixed Sof: C75(0.5) H75A(0.5) H75B(0.5)
5.a Ternary CH refined with riding coordinates:
 C01H(H01H)
5.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C16(H16A,H16B), C17(H17A,H17B), C75(H75A,H75B)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C11(H11), C12(H12), C13(H13), C14(H14),
 C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), C28(H28),
  C29(H29), C30(H30), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36),
 C38(H38), C39(H39), C40(H40), C41(H41), C42(H42), C44(H44), C46(H46), C48(H48),
  C52(H52), C54(H54), C56(H56), C60(H60), C62(H62), C64(H64), C68(H68),
 C70(H70), C72(H72)
5.d Idealised Me refined as rotating group:
 C01R(H01A,H01B,H01C), C02J(H02A,H02B,H02C), C10(H10A,H10B,H10C), C18(H18A,
 H18B,H18C)
;
_shelx_res_checksum              96147
_shelx_hkl_checksum              0
_olex2_submission_special_instructions 'No special instructions were received'