Integrating Activity with Accessibility in Olefin Metathesis: An Unprecedentedly Reactive Ruthenium-Indenylidene Catalyst.
Nascimento, Daniel L.; Gawin, Anna; Gawin, Rafał; Guńka, Piotr A; Zachara, Janusz; Skowerski, Krzysztof; Fogg, Deryn E.; Journal of the American Chemical Society 141 (2019) 10626–10631; doi:10.1021/jacs.9b05362

data_4127639
_publ_section_title
;
 Integrating Activity with Accessibility in Olefin Metathesis: An
 Unprecedentedly Reactive Ruthenium-Indenylidene Catalyst.
;
_journal_issue                   27
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10626
_journal_page_last               10631
_journal_paper_doi               10.1021/jacs.9b05362
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C76 H78 Cl4 N2 Ru2'
_chemical_formula_sum            'C76 H78 Cl4 N2 Ru2'
_chemical_formula_weight         1363.34
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-12-04
_audit_creation_method
;
Olex2 1.2
(compiled May 29 2018 13:30:08 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 105.534(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.2004(7)
_cell_length_b                   13.0402(4)
_cell_length_c                   27.5306(8)
_cell_measurement_reflns_used    11105
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      28.2100
_cell_measurement_theta_min      3.7450
_cell_volume                     6987.1(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_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_temperature      293.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3347
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -98.00  14.00   1.00  300.00    --  -19.49 -77.00 -30.00  112
  2  \w    -46.00  56.00   1.00  300.00    --  -19.49  38.00 -30.00  102
  3  \w    -59.00  53.00   1.00  300.00    --   19.81 -77.00 -90.00  112
  4  \w     56.00 110.00   1.00  300.00    --   19.81 179.00  60.00   54
  5  \w     -4.00  62.00   1.00  300.00    --   19.81 -99.00  60.00   66
  6  \w     -4.00  62.00   1.00  300.00    --   19.81 -99.00 120.00   66
  7  \w    -56.00  -9.00   1.00  300.00    --   19.81 -38.00-120.00   47
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0219022000
_diffrn_orient_matrix_UB_12      -0.0197462000
_diffrn_orient_matrix_UB_13      0.0140421000
_diffrn_orient_matrix_UB_21      0.0120370000
_diffrn_orient_matrix_UB_22      -0.0502910000
_diffrn_orient_matrix_UB_23      -0.0025794000
_diffrn_orient_matrix_UB_31      0.0265033000
_diffrn_orient_matrix_UB_32      0.0065188000
_diffrn_orient_matrix_UB_33      0.0226059000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1093
_diffrn_reflns_av_unetI/netI     0.1051
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            80301
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.000
_diffrn_reflns_theta_min         3.361
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.627
_exptl_absorpt_correction_T_max  0.992
_exptl_absorpt_correction_T_min  0.978
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.296
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2816
_exptl_crystal_size_max          0.138
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.037
_platon_squeeze_details
;
TITL pg108.res in P2(1)/n                                                       
CELL   20.2004   13.0402   27.5306     90.00    105.53     90.00                
SPGR P21/n                                                                      
C101 0.194 0.786 0.492 !       3.18 eA-3                                        
C102 0.642 0.735 0.061 !       2.56 eA-3                                        
C103 0.668 0.705 0.022 !       2.42 eA-3                                        
C104 0.688 0.771 0.015 !       2.35 eA-3                                        
C105 0.152 0.620 0.487 !       2.33 eA-3                                        
C106 0.680 0.808 0.991 !       2.21 eA-3                                        
C107 0.678 0.840 0.047 !       1.96 eA-3                                        
C108 0.687 0.830 0.024 !       1.94 eA-3                                        
C109 0.883 0.361 0.459 !       1.92 eA-3                                        
C110 0.623 0.776 0.063 !       1.91 eA-3                                        
C111 0.713 0.734 0.039 !       1.79 eA-3                                        
C112 0.839 0.348 0.486 !       1.68 eA-3                                        
C113 0.608 0.881 0.992 !       1.67 eA-3                                        
C114 0.400 0.163 0.953 !       1.61 eA-3                                        
C115 0.340 0.171 0.040 !       1.59 eA-3                                        
C116 0.614 0.891 0.015 !       1.56 eA-3                                        
C117 0.810 0.155 0.487 !       1.56 eA-3                                        
Q118 0.133 0.559 0.493 !       1.53 eA-3                                        
C119 0.576 0.952 0.969 !       1.44 eA-3                                        
C120 0.387 0.088 0.041 !       1.42 eA-3                                        
C121 0.900 0.344 0.486 !       1.38 eA-3                                        
C122 0.983 0.405 0.502 !       1.34 eA-3                                        
C123 0.369 0.082 0.062 !       1.33 eA-3                                        
C124 0.438 0.109 0.014 !       1.30 eA-3                                        
C125 0.332 0.078 0.033 !       1.25 eA-3                                        
Q126 0.090 0.530 0.486 !       1.24 eA-3                                        
C127 0.964 0.403 0.462 !       1.24 eA-3                                        
C128 0.432 0.110 0.977 !       1.20 eA-3                                        
Q129 0.226 0.642 0.548 !       1.18 eA-3                                        
C130 0.849 0.371 0.556 !       1.18 eA-3                                        
C131 0.316 0.076 0.061 !       1.17 eA-3                                        
Q132 0.893 0.111 0.462 !       1.17 eA-3                                        
Q133 0.952 0.530 0.469 !       1.16 eA-3                                        
Q134 0.060 0.517 0.408 !       1.13 eA-3                                        
Q135 0.877 0.079 0.555 !       1.11 eA-3                                        
C136 0.012 0.450 0.491 !       1.10 eA-3                                        
C137 0.597 0.955 0.938 !       1.09 eA-3                                        
Q138 0.922 0.200 0.501 !       1.08 eA-3                                        
C139 0.466 0.982 0.041 !       1.08 eA-3                                        
C140 0.343 0.093 0.955 !       1.07 eA-3                                        
C141 0.660 0.828 0.922 !       1.06 eA-3                                        
Q142 0.703 0.861 0.069 !       1.05 eA-3                                        
Q143 0.096 0.497 0.532 !       1.04 eA-3                                        
Q144 0.824 0.420 0.602 !       1.03 eA-3                                        
Q145 0.700 0.906 0.039 !       1.02 eA-3                                        
Q146 0.235 0.765 0.578 !       1.01 eA-3                                        
Q147 0.596 0.751 0.031 !       1.00 eA-3                                        
C148 0.419 0.094 0.069 !       1.00 eA-3                                        
C149 0.876 0.345 0.430 !       0.99 eA-3                                        
Q150 0.095 0.191 0.397 !       0.98 eA-3                                        
Q151 0.923 0.519 0.553 !       0.97 eA-3                                        
Q152 0.251 0.389 0.961 !       0.96 eA-3                                        
C153 1.010 0.501 0.493 !       0.96 eA-3                                        
Q154 0.613 0.809 0.085 !       0.96 eA-3                                        
Q155 0.013 0.597 0.570 !       0.96 eA-3                                        
Q156 0.202 0.065 0.093 !       0.95 eA-3                                        
Q157 0.601 0.729 0.072 !       0.94 eA-3                                        
Q158 0.689 0.733 0.101 !       0.94 eA-3                                        
Q159 0.796 0.266 0.125 !       0.93 eA-3                                        
Q160 0.018 0.830 0.101 !       0.93 eA-3                                        
Q161 0.599 0.472 0.359 !       0.93 eA-3                                        
Q162 0.575 0.432 0.272 !       0.91 eA-3                                        
Q163 0.318 0.409-0.000 !       0.91 eA-3                                        
Q164 0.638 0.668 0.358 !       0.90 eA-3                                        
Q165 0.288 0.064 0.008 !       0.90 eA-3                                        
Q166 0.627 0.687 0.921 !       0.90 eA-3                                        
C167 0.522 0.964 0.032 !       0.90 eA-3                                        
Q168 0.015 0.079 0.961 !       0.89 eA-3                                        
Q169 0.547 0.406 0.117 !       0.89 eA-3                                        
Q170 0.298 0.154 0.047 !       0.89 eA-3                                        
Q171 0.876 0.203 0.939 !       0.88 eA-3                                        
Q172 0.731 0.189 0.056 !       0.88 eA-3                                        
Q173 0.503 0.562 0.102 !       0.88 eA-3                                        
Q174 0.748 0.952 0.014 !       0.88 eA-3                                        
Q175 0.289 0.763 0.516 !       0.88 eA-3                                        
Q176 0.937 0.703 0.983 !       0.88 eA-3                                        
Q177 0.796 0.968 0.234 !       0.87 eA-3                                        
Q178 0.976 0.513 0.568 !       0.87 eA-3                                        
Q179 0.825 0.861 0.783 !       0.87 eA-3                                        
Q180 0.186 0.497 0.406 !       0.87 eA-3                                        
C181 0.948 0.487 0.492 !       0.86 eA-3                                        
Q182 0.781 0.372 0.390 !       0.86 eA-3                                        
Q183 0.418 0.095 0.122 !       0.86 eA-3                                        
Q184 0.212 0.090 0.463 !       0.86 eA-3                                        
C185 0.266 0.341 0.023 !       0.86 eA-3                                        
Q186 0.765 0.168 0.431 !       0.86 eA-3                                        
Q187 0.036 0.748 0.492 !       0.86 eA-3                                        
C188 0.365 0.104 0.092 !       0.85 eA-3                                        
Q189 0.012 0.799 0.258 !       0.85 eA-3                                        
Q190 0.129 0.890 0.485 !       0.85 eA-3                                        
Q191 0.108 0.766 0.601 !       0.85 eA-3                                        
Q192 0.773 0.343 0.352 !       0.85 eA-3                                        
Q193 0.929 0.359 0.430 !       0.85 eA-3                                        
Q194 0.398 0.360 0.001 !       0.85 eA-3                                        
Q195 0.922 0.157 0.445 !       0.85 eA-3                                        
Q196 0.905 0.360 0.804 !       0.84 eA-3                                        
Q197 0.642 0.781 0.540 !       0.84 eA-3                                        
Q198 0.061 0.093 0.250 !       0.84 eA-3                                        
Q199 0.106 0.219 0.368 !       0.84 eA-3                                        
;
_refine_diff_density_max         0.656
_refine_diff_density_min         -0.384
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.962
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     789
_refine_ls_number_reflns         13693
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      0.962
_refine_ls_R_factor_all          0.1068
_refine_ls_R_factor_gt           0.0502
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0234P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0875
_refine_ls_wR_factor_ref         0.1055
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7988
_reflns_number_total             13693
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b05362_si_002.cif
_cod_data_source_block           pg108smart_sq
_cod_database_code               4127639
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ru1 C20 H25 N2 O2'
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.918
_reflns_odcompleteness_completeness 99.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_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
 C23-C22 = C24-C22
 1.519 with sigma of 0.001
 C62-C60 \\sim C61-C60
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
C21: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002
C61 \\sim C62: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C23 \\sim C24: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
4. Others
 Sof(H60C)=Sof(H60D)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(H61C)=1-FVAR(1)
 Sof(H60A)=Sof(H60B)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=FVAR(1)
 Sof(H22C)=Sof(H22D)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=1-FVAR(2)
 Sof(H22A)=Sof(H22B)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C20(H20A,H20B), C22(H22A,H22B), C22(H22C,H22D), C43(H43A,H43B),
 C60(H60A,H60B), C60(H60C,H60D), C63(H63A,H63B)
5.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C16(H16), C17(H17), C18(H18),
 C26(H26), C30(H30), C31(H31), C32(H32), C33(H33), C35(H35), C36(H36), C37(H37),
  C38(H38), C39(H39), C47(H47), C48(H48), C49(H49), C50(H50), C51(H51),
 C56(H56), C57(H57), C58(H58), C66(H66), C70(H70), C71(H71), C72(H72), C73(H73),
  C75(H75), C76(H76), C77(H77), C78(H78), C79(H79)
5.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C21(H21A,H21B,
 H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C45(H45A,H45B,H45C), C52(H52A,
 H52B,H52C), C53(H53A,H53B,H53C), C61(H61A,H61B,H61C), C62(H62A,H62B,H62C),
 C64(H64A,H64B,H64C)
;
_platon_squeeze_void_probe_radius 1.20
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.170
_oxdiff_exptl_absorpt_empirical_full_min 0.906