Living Polymerization Caught in the Act: Direct Observation of an Arrested Intermediate in Metathesis Polymerization.
Song, Jung-Ah; Park, Bohyun; Kim, Soohyung; Kang, Cheol; Lee, Dongwhan; Baik, Mu-Hyun; Grubbs, Robert H.; Choi, Tae-Lim; Journal of the American Chemical Society 141 (2019) 10039–10047; doi:10.1021/jacs.9b04019

data_4128266
_publ_section_title
;
 Living Polymerization Caught in the Act: Direct Observation of an
 Arrested Intermediate in Metathesis Polymerization.
;
_journal_issue                   25
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10039
_journal_page_last               10047
_journal_paper_doi               10.1021/jacs.9b04019
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C49 H50 Cl2 N4 O2 Ru, C H2 Cl2'
_chemical_formula_sum            'C50 H52 Cl4 N4 O2 Ru'
_chemical_formula_weight         983.82
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-02-06
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.8170(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.91960(10)
_cell_length_b                   21.86780(10)
_cell_length_c                   21.50840(10)
_cell_measurement_reflns_used    34793
_cell_measurement_temperature    101(2)
_cell_measurement_theta_max      73.6500
_cell_measurement_theta_min      2.8970
_cell_volume                     4582.70(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_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 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      101(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2262
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -96.00  -2.00   1.00    1.19    --  -41.82 125.00-120.00   94
  2  \w     14.00 115.00   1.00    1.19    --   41.82  57.00  60.00  101
  3  \w    -38.00  83.00   1.00    1.19    --   41.82 -19.00   0.00  121
  4  \w     23.00  98.00   1.00    1.19    --   41.82-125.00-180.00   75
  5  \w     33.00 122.00   1.00    4.77    --  105.87-125.00 150.00   89
  6  \w     77.00 178.00   1.00    4.77    --  105.87  61.00 -90.00  101
  7  \w     77.00 178.00   1.00    4.77    --  105.87  61.00  30.00  101
  8  \w     94.00 178.00   1.00    4.77    --  105.87 125.00  30.00   84
  9  \w     34.00 135.00   1.00    4.77    --  105.87 -61.00 -90.00  101
 10  \w     77.00 178.00   1.00    4.77    --  105.87  61.00 -30.00  101
 11  \w      9.00 118.00   1.00    1.19    --   41.82  77.00-150.00  109
 12  \w     17.00 116.00   1.00    1.19    --   41.82  38.00-180.00   99
 13  \w      9.00 118.00   1.00    1.19    --   41.82  77.00 -60.00  109
 14  \w     34.00 135.00   1.00    4.77    --  105.87 -61.00 120.00  101
 15  \w     77.00 178.00   1.00    4.77    --  105.87  61.00  90.00  101
 16  \w     73.00 130.00   1.00    4.77    --  105.87  77.00-150.00   57
 17  \w     53.00 178.00   1.00    4.77    --  105.87  15.00-150.00  125
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1028902000
_diffrn_orient_matrix_UB_12      0.0378765000
_diffrn_orient_matrix_UB_13      0.0473249000
_diffrn_orient_matrix_UB_21      -0.0190995000
_diffrn_orient_matrix_UB_22      -0.0439758000
_diffrn_orient_matrix_UB_23      0.0536467000
_diffrn_orient_matrix_UB_31      0.1185143000
_diffrn_orient_matrix_UB_32      -0.0399303000
_diffrn_orient_matrix_UB_33      -0.0141751000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0259
_diffrn_reflns_av_unetI/netI     0.0154
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            46526
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.765
_diffrn_reflns_theta_min         2.908
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.262
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57361
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.29d (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.426
_exptl_crystal_description       plate
_exptl_crystal_F_000             2032
_exptl_crystal_size_max          0.345
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.107
_refine_diff_density_max         0.410
_refine_diff_density_min         -0.452
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     587
_refine_ls_number_reflns         9183
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0225
_refine_ls_R_factor_gt           0.0223
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0188P)^2^+3.9992P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0532
_refine_ls_wR_factor_ref         0.0533
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9069
_reflns_number_total             9183
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b04019_si_003.cif
_cod_data_source_block           exp_1179
_cod_database_code               4128266
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         CHNOClRu
_shelx_estimated_absorpt_t_max   0.603
_shelx_estimated_absorpt_t_min   0.264
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 Cl3'-C50 \\sim Cl3-C50
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Cl4 \\sim Cl4': within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.005
Cl3 \\sim Cl3': within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.01
4. Others
 Sof(Cl3')=Sof(Cl4')=Sof(H50C)=Sof(H50D)=1-FVAR(1)
 Sof(Cl3)=Sof(Cl4)=Sof(H50A)=Sof(H50B)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B),
 C50(H50A,H50B), C50(H50C,H50D)
5.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C8(H8), C15(H15), C17(H17), C28(H28), C29(H29), C30(H30), C31(H31),
 C32(H32), C38(H38), C39(H39), C40(H40), C41(H41), C42(H42), C45(H45), C46(H46),
  C47(H47), C48(H48), C49(H49)
5.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C)
;
_shelx_res_checksum              58389
_shelx_hkl_checksum              45719
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.688
_oxdiff_exptl_absorpt_empirical_full_min 0.745