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_4517304
_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 H48.89 N2 Pd, B F4, C H Cl3'
_chemical_formula_sum            'C38 H49.88 B Cl3 F4 N2 Pd'
_chemical_formula_weight         834.24
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_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                90
_cell_angle_beta                 101.1710(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.2879(6)
_cell_length_b                   12.5324(7)
_cell_length_c                   25.7400(14)
_cell_measurement_reflns_used    9947
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      28.24
_cell_measurement_theta_min      2.29
_cell_volume                     3888.8(4)
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      120
_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  0.0696
_diffrn_reflns_av_unetI/netI     0.0440
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            79902
_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         30.536
_diffrn_reflns_theta_min         1.613
_exptl_absorpt_coefficient_mu    0.732
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6802
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0638 before and 0.0576 after correction.
The Ratio of minimum to maximum transmission is 0.9117.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.425
_exptl_crystal_description       prism
_exptl_crystal_F_000             1720
_exptl_crystal_size_max          0.320
_exptl_crystal_size_mid          0.250
_exptl_crystal_size_min          0.200
_refine_diff_density_max         1.823
_refine_diff_density_min         -2.107
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.105
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     541
_refine_ls_number_reflns         11877
_refine_ls_number_restraints     197
_refine_ls_restrained_S_all      1.127
_refine_ls_R_factor_all          0.1039
_refine_ls_R_factor_gt           0.0843
_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^)+(0.0301P)^2^+28.3365P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1769
_refine_ls_wR_factor_ref         0.1854
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9521
_reflns_number_total             11877
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b04686_si_004.cif
_cod_data_source_block           '[(6Dipp)Pd(cinn)]+BF4-'
_cod_depositor_comments
'Adding full bibliography for 4517302--4517305.cif.'
_cod_database_code               4517304
_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
 Cl1-C1S \\sim Cl3S-C1S
 with sigma of 0.005
 C31A-C30A \\sim C31-C30
 with sigma of 0.005
 F4A-F2A \\sim F4-F2 \\sim F3-F2 \\sim F3A-F2A
 with sigma of 0.01
 B1-F4A \\sim B1-F4 \\sim B1-F3 \\sim B1-F3A \\sim B1-F2A \\sim B1-F2 \\sim
B1-F1
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Cl1 \\sim Cl3S: within 1.7A with sigma of 0.005 and sigma for terminal atoms of
0.005
F4A \\sim F2 \\sim F2A \\sim F3 \\sim F3A \\sim F4: within 1.7A with sigma of
0.005 and sigma for terminal atoms of 0.005
C32 \\sim C33 \\sim C33A \\sim C34 \\sim C34A \\sim C35A \\sim C35 \\sim C36
\\sim C36A \\sim C37 \\sim C37A: within 1.7A with sigma of 0.005 and sigma for
terminal atoms of 0.005
4. Rigid body (RIGU) restrains
 Cl3S, Cl1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H1SA)=Sof(Cl1)=1-FVAR(1)
 Sof(H1S)=Sof(H31)=Sof(Cl3S)=FVAR(1)
 Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31A)=1-FVAR(2)
 Sof(C31)=Sof(C30)=Sof(H30)=FVAR(2)
 Sof(F2A)=Sof(F3A)=Sof(F4A)=1-FVAR(3)
 Sof(F2)=Sof(F3)=Sof(F4)=FVAR(3)
 Sof(C33A)=Sof(H33A)=Sof(C34A)=Sof(H34A)=Sof(C35A)=Sof(H35A)=Sof(C36A)=
 Sof(H36A)=Sof(C37A)=Sof(H37A)=1-FVAR(4)
 Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35)=Sof(C36)=Sof(H36)=
 Sof(C37)=Sof(H37)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C23(H23), C26(H26), C14(H14), C11(H11), C1S(H1S), C1S(H1SA), C31(H31),
 C30(H30), C30A(H30A), C31A(H31A)
6.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C2(H2A,H2B), C1(H1A,H1B), C29(H29A,H29B)
6.c Aromatic/amide H refined with riding coordinates:
 C21(H21), C20(H20), C9(H9), C19(H19), C7(H7), C8(H8), C33(H33), C34(H34),
 C35(H35), C36(H36), C37(H37), C33A(H33A), C34A(H34A), C35A(H35A), C36A(H36A),
 C37A(H37A)
6.d Fitted hexagon refined as free rotating group:
 C32(C33,C34,C35,C36,C37)
6.e Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C24(H24A,H24B,H24C), C28(H28A,H28B,
 H28C), C16(H16A,H16B,H16C), C12(H12A,H12B,H12C), C15(H15A,H15B,H15C), C13(H13A,
 H13B,H13C)
;
_shelx_res_checksum              49128
_shelx_hkl_checksum              92233
_olex2_submission_special_instructions 'No special instructions were received'