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_4517305
_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         'C38 H51 N2 Pd, C32 H12 B F24'
_chemical_formula_sum            'C70 H63 B F24 N2 Pd'
_chemical_formula_weight         1505.43
_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             2019-06-28
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                77.667(2)
_cell_angle_beta                 83.865(2)
_cell_angle_gamma                74.979(2)
_cell_formula_units_Z            2
_cell_length_a                   12.7466(11)
_cell_length_b                   13.1407(11)
_cell_length_c                   21.5974(19)
_cell_measurement_reflns_used    9432
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      30
_cell_measurement_theta_min      3
_cell_volume                     3408.2(5)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      120
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_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  0.0683
_diffrn_reflns_av_unetI/netI     0.1172
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            32675
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.000
_diffrn_reflns_theta_min         1.635
_exptl_absorpt_coefficient_mu    0.381
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'APEX2 (Bruker, 2005)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.467
_exptl_crystal_description       prism
_exptl_crystal_F_000             1528
_exptl_crystal_size_max          0.280
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.180
_exptl_transmission_factor_max   0.7461
_exptl_transmission_factor_min   0.6602
_refine_diff_density_max         2.155
_refine_diff_density_min         -0.916
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.011
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1015
_refine_ls_number_reflns         16401
_refine_ls_number_restraints     243
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.1379
_refine_ls_R_factor_gt           0.0788
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0739P)^2^+9.2205P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1746
_refine_ls_wR_factor_ref         0.2071
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9638
_reflns_number_total             16401
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b04686_si_003.cif
_cod_data_source_block           '[(7Dipp)Pd(cinn)]+BARF-'
_cod_depositor_comments
'Adding full bibliography for 4517302--4517305.cif.'
_cod_database_code               4517305
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F19-F20 \\sim F19-F21 \\sim F20-F21 \\sim F19A-F20A \\sim F19A-F21A \\sim
F20A-F21A
 with sigma of 0.01
 C31A-F19 \\sim C31A-F20 \\sim C31A-F21 \\sim C31A-C27A \\sim C31A-F19A \\sim
C31A-F20A \\sim C31A-F21A
 with sigma of 0.005
 F7-F8 \\sim F7-F9 \\sim F8-F9 \\sim F7A-F8A \\sim F7A-F9A \\sim F8A-F9A
 with sigma of 0.01
 C15A-C11A \\sim C15A-F7 \\sim C15A-F8 \\sim C15A-F9 \\sim C15A-F7A \\sim
C15A-F8A \\sim C15A-F9A
 with sigma of 0.005
 F13-F14 \\sim F13-F15 \\sim F14-F15 \\sim F14A-F13A \\sim F14A-F15A \\sim
F13A-F15A
 with sigma of 0.01
 C23A-F13 \\sim C23A-F14 \\sim C23A-F15 \\sim C23A-C19A \\sim C23A-F14A \\sim
C23A-F13A \\sim C23A-F15A
 with sigma of 0.005
 F4-F5 \\sim F4-F6 \\sim F5-F6
 with sigma of 0.01
 C8A-C5A \\sim C8A-F4 \\sim C8A-F5 \\sim C8A-F6
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
F20A \\sim F19 \\sim F19A \\sim F21 \\sim F21A \\sim F20: within 1.7A with
sigma of 0.005 and sigma for terminal atoms of 0.005
F7A \\sim F7 \\sim F9 \\sim F9A \\sim F8 \\sim F8A: within 1.7A with sigma of
0.005 and sigma for terminal atoms of 0.005
F6 \\sim F5 \\sim F4: within 1.7A with sigma of 0.005 and sigma for terminal
atoms of 0.005
F14 \\sim F15A \\sim F15 \\sim F13A \\sim F13 \\sim F14A: within 1.7A with
sigma of 0.005 and sigma for terminal atoms of 0.005
F4 \\sim F6 \\sim F5: within 1.7A with sigma of 0.005 and sigma for terminal
atoms of 0.05
C8A: within 1.7A with sigma of 0.005 and sigma for terminal atoms of 0.005
F5: within 1.7A with sigma of 0.005 and sigma for terminal atoms of 0.005
Uanis(F4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F4) \\sim Ueq, Uanis(F5) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 C8A, F4, F5, F6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F6, F4, F5, C8A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H31A)=Sof(C32')=Sof(H32')=Sof(C33')=Sof(C38')=Sof(H38')=Sof(C37')=
 Sof(H37')=Sof(C36')=Sof(H36')=Sof(C35')=Sof(H35')=Sof(C34')=Sof(H34')=1-FVAR(1)
 Sof(H31)=Sof(C32)=Sof(H32)=Sof(C33)=Sof(C38)=Sof(H38)=Sof(C37)=Sof(H37)=
 Sof(C36)=Sof(H36)=Sof(C35)=Sof(H35)=Sof(C34)=Sof(H34)=FVAR(1)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=1-FVAR(2)
 Sof(F19)=Sof(F20)=Sof(F21)=FVAR(2)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(3)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(3)
 Sof(F14A)=Sof(F13A)=Sof(F15A)=1-FVAR(4)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C24(H24), C27(H27), C31(H31), C31(H31A), C32(H32),
 C32'(H32')
6.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C30(H30A,H30B)
6.c Aromatic/amide H refined with riding coordinates:
 C2A(H2AA), C4A(H4AA), C6A(H6A), C8(H8), C9(H9), C10A(H10A), C10(H10),
 C12A(H12A), C14A(H14D), C18A(H18A), C20A(H20A), C20(H20), C21(H21), C22A(H22A),
  C22(H22), C26A(H26D), C28A(H28D), C30A(H30C), C38(H38), C37(H37), C36(H36),
 C35(H35), C34(H34), C38'(H38'), C37'(H37'), C36'(H36'), C35'(H35'), C34'(H34')
6.d Fitted hexagon refined as free rotating group:
 C33(C38,C37,C36,C35,C34), C33'(C38',C37',C36',C35',C34')
6.e Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,
 H29B,H29C)
;
_shelx_res_checksum              69246
_shelx_hkl_checksum              55603
_olex2_submission_special_instructions 'No special instructions were received'