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_4517302
_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, C32 H12 B F24'
_chemical_formula_sum            'C69 H61 B F24 N2 Pd'
_chemical_formula_weight         1491.40
_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   mixed
_audit_creation_date             2019-07-01
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                85.1110(10)
_cell_angle_beta                 78.3280(10)
_cell_angle_gamma                76.4630(10)
_cell_formula_units_Z            2
_cell_length_a                   12.7592(7)
_cell_length_b                   12.8409(7)
_cell_length_c                   21.6356(12)
_cell_measurement_reflns_used    4683
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      23.05
_cell_measurement_theta_min      2.30
_cell_volume                     3372.4(3)
_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      120.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_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  0.0664
_diffrn_reflns_av_unetI/netI     0.1008
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            45331
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.000
_diffrn_reflns_theta_min         1.765
_exptl_absorpt_coefficient_mu    0.384
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6667
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0637 before and 0.0506 after correction.
The Ratio of minimum to maximum transmission is 0.8936.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.469
_exptl_crystal_description       prism
_exptl_crystal_F_000             1512
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.250
_exptl_crystal_size_min          0.200
_exptl_transmission_factor_max   0.746
_exptl_transmission_factor_min   0.667
_refine_diff_density_max         0.748
_refine_diff_density_min         -1.218
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.006
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     996
_refine_ls_number_reflns         19644
_refine_ls_number_restraints     120
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.1179
_refine_ls_R_factor_gt           0.0593
_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^)+(0.0503P)^2^+1.0888P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1191
_refine_ls_wR_factor_ref         0.1473
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11191
_reflns_number_total             19644
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b04686_si_005.cif
_cod_data_source_block           '[(6Dipp)Pd(cinn)]+BF4-'
_cod_depositor_comments
'Adding full bibliography for 4517302--4517305.cif.'
_cod_database_code               4517302
_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
 F13A-F14A \\sim F13A-F15A \\sim F14A-F15A \\sim F14B-F15B \\sim F14B-F13B
\\sim F15B-F13B
 with sigma of 0.01
 C23A-C19A \\sim C23A-F13A \\sim C23A-F14A \\sim C23A-F15A \\sim C23A-F14B
\\sim C23A-F15B \\sim C23A-
 F13B
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
F14A \\sim F14B \\sim F15A \\sim F15B \\sim F13A \\sim F13B: within 1.7A with
sigma of 0.005 and sigma for terminal atoms of 0.005
C36' \\sim C36 \\sim C35 \\sim C35' \\sim C34 \\sim C34': within 1.7A with
sigma of 0.005 and sigma for terminal atoms of 0.005
4. Others
 Sof(H2BC)=Sof(H2BD)=Sof(C3')=Sof(H3'A)=Sof(H3'B)=Sof(H4BC)=Sof(H4BD)=1-FVAR(1)
 Sof(H2AA)=Sof(H2AB)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H4AA)=Sof(H4AB)=FVAR(1)
 Sof(H29C)=Sof(H29D)=Sof(C30')=Sof(H30')=Sof(C31')=Sof(H31')=1-FVAR(2)
 Sof(H29A)=Sof(H29B)=Sof(C31)=Sof(H31)=Sof(C30)=Sof(H30)=FVAR(2)
 Sof(F14B)=Sof(F15B)=Sof(F13B)=1-FVAR(3)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=FVAR(3)
 Sof(C32')=Sof(C33')=Sof(H33')=Sof(C34')=Sof(H34')=Sof(C35')=Sof(H35')=
 Sof(C36')=Sof(H36')=Sof(C37')=Sof(H37')=1-FVAR(4)
 Sof(C32)=Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35)=Sof(C36)=
 Sof(H36)=Sof(C37)=Sof(H37)=FVAR(4)
5.a Ternary CH refined with riding coordinates:
 C11(H11), C14(H14), C23(H23), C26(H26), C31(H31), C30(H30), C30'(H30'),
 C31'(H31')
5.b Secondary CH2 refined with riding coordinates:
 C2(H2BC,H2BD), C3(H3A,H3B), C3'(H3'A,H3'B), C4(H4BC,H4BD), C29(H29A,H29B),
 C29(H29C,H29D)
5.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C19(H19), C20(H20), C21(H21), C33(H33), C34(H34),
 C35(H35), C36(H36), C37(H37), C2A(H2A), C4A(H4A), C6A(H6A), C10A(H10A),
 C12A(H12D), C14A(H14A), C18A(H18A), C20A(H20A), C22A(H22A), C26A(H26A),
 C28A(H28D), C30A(H30A), C33'(H33'), C34'(H34'), C35'(H35'), C36'(H36'),
 C37'(H37')
5.d Fitted hexagon refined as free rotating group:
 C32(C33,C34,C35,C36,C37)
5.e Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C28(H28A,
 H28B,H28C)
;
_shelx_res_checksum              37698
_shelx_hkl_checksum              14078
_olex2_submission_special_instructions 'No special instructions were received'