Origins of initiation rate differences in ruthenium olefin metathesis catalysts containing chelating benzylidenes.
Engle, Keary M.; Lu, Gang; Luo, Shao-Xiong; Henling, Lawrence M.; Takase, Michael K.; Liu, Peng; Houk, K. N.; Grubbs, Robert H.; Journal of the American Chemical Society 137 (2015) 5782–5792; doi:10.1021/jacs.5b01144

data_4129362
_publ_section_title
;
 Origins of initiation rate differences in ruthenium olefin metathesis
 catalysts containing chelating benzylidenes.
;
_journal_issue                   17
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5782
_journal_page_last               5792
_journal_paper_doi               10.1021/jacs.5b01144
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety         'C38 H46 Cl2 N2 O Ru'
_chemical_formula_sum            'C38 H46 Cl2 N2 O Ru'
_chemical_formula_weight         718.74
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-02-03
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736),
 SHELXL-2014,
 and manual edit
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.3436(8)
_cell_length_b                   23.1535(9)
_cell_length_c                   15.3598(6)
_cell_measurement_reflns_used    9220
_cell_measurement_temperature    100
_cell_measurement_theta_max      37.54
_cell_measurement_theta_min      2.65
_cell_volume                     6879.2(5)
_computing_cell_refinement       'SAINT V8.34A (Bruker-AXS, 2007)'
_computing_data_collection       'APEX2 2013.10-0 (Bruker-AXS, 2007)'
_computing_data_reduction        'SAINT V8.34A (Bruker-AXS, 2007)'
_computing_molecular_graphics    'DIAMOND 3 (Crystal Impact, 1999)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/1 (Sheldrick, 2014)'
_computing_structure_solution    'XT (Sheldrick, 2012)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 8.33
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.986
_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  0.0578
_diffrn_reflns_av_unetI/netI     0.0360
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       43
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            479545
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         41.753
_diffrn_reflns_theta_min         1.908
_diffrn_source_current           30
_diffrn_source_power             1.5
_diffrn_source_target            Mo
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.643
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8728
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0664 before and 0.0598 after correction.
The Ratio of minimum to maximum transmission is 0.8728.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            green
_exptl_crystal_density_diffrn    1.388
_exptl_crystal_description       plate
_exptl_crystal_F_000             2992
_exptl_crystal_size_max          0.51
_exptl_crystal_size_mid          0.42
_exptl_crystal_size_min          0.11
_refine_diff_density_max         2.360
_refine_diff_density_min         -1.283
_refine_diff_density_rms         0.119
_refine_ls_abs_structure_details
;
 Flack x determined using 13251 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.025(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.534
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     805
_refine_ls_number_reflns         46262
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.534
_refine_ls_R_factor_all          0.0862
_refine_ls_R_factor_gt           0.0445
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0300P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0897
_refine_ls_wR_factor_ref         0.1027
_reflns_Friedel_coverage         0.928
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.965
_reflns_number_gt                31719
_reflns_number_total             46262
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b01144_si_006.cif
_cod_data_source_block           a14014
_cod_database_code               4129362
_shelxl_version_number           2014-1
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.735
_refine_ls_abs_structure_hooft   -0.032(4)
_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.a Ternary CH refined with riding coordinates:
 C31(H31), C33(H33), C35(H35), C33B(H33B), C31B(H31B), C35B(H35B)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C30(H30A,H30B), C32(H32A,H32B), C34(H34A,H34B),
 C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B), C2B(H2BA,H2BB), C3B(H3BA,H3BB),
  C37B(H37C,H37D), C32B(H32C,H32D), C38B(H38C,H38D), C30B(H30C,H30D), C34B(H34C,
 H34D), C36B(H36C,H36D)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C8(H8), C15(H15), C17(H17), C22(H22), C24(H24), C25(H25), C26(H26),
 C27(H27), C8B(H8B), C6B(H6B), C17B(H17B), C15B(H15B), C22B(H22B), C24B(H24B),
 C25B(H25B), C26B(H26B), C27B(H27B)
2.d 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), C12B(H12D,H12E,H12F),
 C11B(H11D,H11E,H11F), C10B(H10D,H10E,H10F), C21B(H21D,H21E,H21F), C20B(H20D,
 H20E,H20F), C19B(H19D,H19E,H19F)
;