Cyclometalated Z-Selective Ruthenium Metathesis Catalysts with Modified N-Chelating Groups
Herbert, Myles B.; Suslick, Benjamin A.; Liu, Peng; Zou, Lufeng; Dornan, Peter K.; Houk, K. N.; Grubbs, Robert H.; Organometallics 34 (2015) 2858–; doi:10.1021/acs.organomet.5b00185

data_4087496
_publ_section_title
;
 Cyclometalated Z-Selective Ruthenium Metathesis Catalysts with Modified
 N-Chelating Groups
;
_journal_issue                   12
_journal_name_full               Organometallics
_journal_page_first              2858
_journal_paper_doi               10.1021/acs.organomet.5b00185
_journal_volume                  34
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C32 H44 Cl2 N2 O Ru, 0.5(C4 H10 O)'
_chemical_formula_sum            'C34 H49 Cl2 N2 O1.5 Ru'
_chemical_formula_weight         681.72
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-08-22
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862,
 SHELXL-2014,
 and manual edit
;
_cell_angle_alpha                90
_cell_angle_beta                 90.6059(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.9034(5)
_cell_length_b                   10.1304(3)
_cell_length_c                   18.8525(5)
_cell_measurement_reflns_used    9594
_cell_measurement_temperature    100
_cell_measurement_theta_max      78.80
_cell_measurement_theta_min      2.47
_cell_volume                     3419.06(17)
_computing_cell_refinement       'SAINT V8.34A (Bruker-AXS, 2007)'
_computing_data_collection       'APEX2 2014.7-1 (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-2014/6 (Sheldrick, 2014)'
_computing_structure_solution    'XT-2014/3 (Sheldrick, 2012)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_device_type  'Bruker Kappa Duo Photon 100 CMOS'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'Incoatech ImuS multilayer optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0358
_diffrn_reflns_av_unetI/netI     0.0361
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            59079
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.947
_diffrn_reflns_theta_full        67.500
_diffrn_reflns_theta_max         78.945
_diffrn_reflns_theta_min         2.344
_diffrn_source                   'ImuS micro-focus sealed tube'
_diffrn_source_current           1
_diffrn_source_power             0.05
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.366
_exptl_absorpt_correction_T_max  0.6688
_exptl_absorpt_correction_T_min  0.4920
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/3 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.0889 before and 0.0737 after correction.
The Ratio of minimum to maximum transmission is 0.7356.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.324
_exptl_crystal_description       block
_exptl_crystal_F_000             1428
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.767
_refine_diff_density_min         -0.526
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details
;
 Flack x determined using 6084 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
 At room temperature these crystals are badly disordered
(the cyclic alkyl group bonded to an N atom) in space group P4(3).
Cooling them results in a phase transition to space group P2(1).
This transition is accompanied by twinning in all cases but this
specific crystal.
;
_refine_ls_abs_structure_Flack   0.056(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.122
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     746
_refine_ls_number_reflns         13984
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.122
_refine_ls_R_factor_all          0.0263
_refine_ls_R_factor_gt           0.0255
_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^)+(0.0092P)^2^+2.6010P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0600
_refine_ls_wR_factor_ref         0.0603
_reflns_Friedel_coverage         0.823
_reflns_Friedel_fraction_full    0.968
_reflns_Friedel_fraction_max     0.907
_reflns_number_gt                13728
_reflns_number_total             13984
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00185_si_003.cif
_cod_data_source_block           p14001
_cod_original_formula_sum        'C34 H49 Cl2 N2 O1.50 Ru'
_cod_database_code               4087496
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.399
_shelx_estimated_absorpt_t_min   0.287
_refine_ls_abs_structure_hooft   0.041(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.a Ternary CH refined with riding coordinates:
 C5(H5), C8(H8), C10(H10), C30(H30), C5B(H5B), C8B(H8B), C10B(H10B), C30B(H30B)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C6(H6A,H6B), C7(H7A,H7B), C9(H9A,H9B),
 C2B(H2BA,H2BB), C3B(H3BA,H3BB), C4B(H4BA,H4BB), C6B(H6BA,H6BB), C7B(H7BA,H7BB),
  C9B(H9BA,H9BB), C34(H34A,H34B), C35(H35A,H35B)
2.c Aromatic/amide H refined with riding coordinates:
 C16(H16), C18(H18), C23(H23), C25(H25), C26(H26), C27(H27), C28(H28),
 C16B(H16B), C18B(H18B), C23B(H23B), C25B(H25B), C26B(H26B), C27B(H27B),
 C28B(H28B)
2.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C),
 C12B(H12D,H12E,H12F), C13B(H13D,H13E,H13F), C20B(H20D,H20E,H20F), C21B(H21D,
 H21E,H21F), C22B(H22D,H22E,H22F), C31B(H31D,H31E,H31F), C32B(H32D,H32E,H32F),
 C33(H33A,H33B,H33C), C36(H36A,H36B,H36C)
;
_olex2_submission_special_instructions 'No special instructions were received'