Polymerization of 5-Alkylidene-2-norbornenes with Highly Active Pd‒N-Heterocyclic Carbene Complex Catalysts: Catalyst Structure‒Activity Relationships
Bermesheva, Evgeniya V.; Wozniak, Alyona I.; Andreyanov, Fedor A.; Karpov, Gleb O.; Nechaev, Mikhail S.; Asachenko, Andrey F.; Topchiy, Maxim A.; Melnikova, Elizaveta K.; Nelyubina, Yulia V.; Gribanov, Pavel S.; Bermeshev, Maxim V.; ACS Catalysis  (2020) 1663–1678; doi:10.1021/acscatal.9b04686

data_4517303
_publ_section_title
;
 Polymerization of 5-Alkylidene-2-norbornenes with Highly Active
 Pd--N-Heterocyclic Carbene Complex Catalysts: Catalyst
 Structure--Activity Relationships
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              1663
_journal_page_last               1678
_journal_paper_doi               10.1021/acscatal.9b04686
_journal_year                    2020
_chemical_formula_moiety         'C37 H49 N2 Pd, F6 Sb'
_chemical_formula_sum            'C37 H49 F6 N2 Pd Sb'
_chemical_formula_weight         863.93
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-06-28
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.818(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.8611(16)
_cell_length_b                   16.2187(19)
_cell_length_c                   16.4272(19)
_cell_measurement_reflns_used    6426
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      30
_cell_measurement_theta_min      3
_cell_volume                     3674.0(7)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      120
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX2 DUO CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0650
_diffrn_reflns_av_unetI/netI     0.0493
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            42026
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.000
_diffrn_reflns_theta_min         1.477
_exptl_absorpt_coefficient_mu    1.283
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'APEX2 (Bruker, 2005)'
_exptl_crystal_density_diffrn    1.562
_exptl_crystal_description       prism
_exptl_crystal_F_000             1744
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.180
_exptl_crystal_size_min          0.110
_exptl_transmission_factor_max   0.4330
_exptl_transmission_factor_min   0.3704
_refine_diff_density_max         0.625
_refine_diff_density_min         -0.706
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     488
_refine_ls_number_reflns         8877
_refine_ls_number_restraints     97
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0572
_refine_ls_R_factor_gt           0.0381
_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^)+(0.0249P)^2^+5.7052P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0752
_refine_ls_wR_factor_ref         0.0839
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6827
_reflns_number_total             8877
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b04686_si_002.cif
_cod_data_source_block           a
_cod_depositor_comments
'Adding full bibliography for 4517302--4517305.cif.'
_cod_database_code               4517303
_shelx_shelxl_version_number     2018/3
_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
 F1A-F3A \\sim F1A-F5A \\sim F2-F3 \\sim F2-F5 \\sim F1-F3 \\sim F1-F5 \\sim
F3A-F2A \\sim F2A-F5A
 with sigma of 0.01
 Sb1-F1A \\sim Sb1-F2 \\sim Sb1-F1 \\sim Sb1-F3A \\sim Sb1-F2A \\sim Sb1-F3
\\sim Sb1-F5 \\sim Sb1-F5A ~
 Sb1-F4 \\sim Sb1-F6
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
F3 \\sim F3A \\sim F2 \\sim F2A \\sim F5 \\sim F1A \\sim F1 \\sim F5A \\sim F4
\\sim F6: within 1.7A with sigma of 0.005 and sigma for terminal atoms of 0.005
4. Others
 Sof(H29C)=Sof(H29D)=Sof(C30')=Sof(H30')=Sof(C31')=Sof(H31')=1-FVAR(1)
 Sof(H29A)=Sof(H29B)=Sof(C31)=Sof(H31)=Sof(C30)=Sof(H30)=FVAR(1)
 Sof(F2A)=Sof(F5A)=Sof(F1A)=Sof(F3A)=1-FVAR(2)
 Sof(F2)=Sof(F3)=Sof(F5)=Sof(F1)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C17(H17), C20(H20), C23(H23), C26(H26), C31(H31), C30(H30), C30'(H30'),
 C31'(H31')
5.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C4(H4A,H4B), C29(H29C,H29D), C29(H29A,H29B)
5.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C13(H13), C14(H14), C15(H15), C33(H33), C34(H34),
 C35(H35), C36(H36), C37(H37)
5.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C28(H28A,
 H28B,H28C)
;
_shelx_res_checksum              90498
_shelx_hkl_checksum              62862
_olex2_submission_special_instructions 'No special instructions were received'