Dynamic π-Bonding of Imidazolyl Substituent in a Formally 16-Electron Cp*Ru(κ2-P,N)+ Catalyst Allows Dramatic Rate Increases in (E)-Selective Monoisomerization of Alkenes
Paulson, Erik R.; Moore, Curtis E.; Rheingold, Arnold L.; Pullman, David P.; Sindewald, Ryan W.; Cooksy, Andrew L.; Grotjahn, Douglas B.; ACS Catalysis 9 (2019) 7217–; doi:10.1021/acscatal.8b04345

data_4514659
_publ_section_title
;
 Dynamic \p-Bonding of Imidazolyl Substituent in a Formally 16-Electron
 Cp*Ru(\k2-P,N)+ Catalyst Allows Dramatic Rate Increases in (E)-Selective
 Monoisomerization of Alkenes
;
_journal_issue                   8
_journal_name_full               'ACS Catalysis'
_journal_page_first              7217
_journal_paper_doi               10.1021/acscatal.8b04345
_journal_volume                  9
_journal_year                    2019
_chemical_formula_moiety         'C20 H34 Cl N2 P Ru'
_chemical_formula_sum            'C20 H34 Cl N2 P Ru'
_chemical_formula_weight         469.98
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-10-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.975(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.3641(6)
_cell_length_b                   15.0206(7)
_cell_length_c                   10.9602(6)
_cell_measurement_reflns_used    3172
_cell_measurement_temperature    100
_cell_measurement_theta_max      24.20
_cell_measurement_theta_min      2.69
_cell_volume                     2194.82(19)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'APEX2 v2013.6-2 (Bruker, 2013)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 8.0
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_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  0.0540
_diffrn_reflns_av_unetI/netI     0.0686
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            16954
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.289
_diffrn_reflns_theta_min         2.042
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.915
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6792
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0517 before and 0.0436 after correction. The Ratio of minimum to maximum transmission is 0.9108. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.422
_exptl_crystal_description       block
_exptl_crystal_F_000             976
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.248
_refine_diff_density_min         -0.834
_refine_diff_density_rms         0.137
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     314
_refine_ls_number_reflns         5418
_refine_ls_number_restraints     420
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0773
_refine_ls_R_factor_gt           0.0501
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0359P)^2^+6.8334P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1004
_refine_ls_wR_factor_ref         0.1120
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4039
_reflns_number_total             5418
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b04345_si_006.cif
_cod_data_source_block           Complex7
_cod_database_code               4514659
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.898
_shelx_estimated_absorpt_t_min   0.758
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C3) = Uanis(C2')
Uanis(C2') = Uanis(C2)
Uanis(C4) = Uanis(C3')
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(C3')=Sof(C4')=Sof(C5')=Sof(C1')=Sof(C2')=Sof(C6')=Sof(H6'A)=Sof(H6'B)=
 Sof(H6'C)=Sof(C7')=Sof(H7'A)=Sof(H7'B)=Sof(H7'C)=Sof(C8')=Sof(H8'A)=Sof(H8'B)=
 Sof(H8'C)=Sof(C9')=Sof(H9'A)=Sof(H9'B)=Sof(H9'C)=Sof(C10')=Sof(H10D)=Sof(H10E)=
 Sof(H10F)=1-FVAR(1)
 Sof(C1)=Sof(C2)=Sof(C3)=Sof(C4)=Sof(C5)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=
 Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C25(H25), C29(H29)
5.b Aromatic/amide H refined with riding coordinates:
 C22(H22), C21(H21)
5.c Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C24(H24A,H24B,
 H24C), C28(H28A,H28B,H28C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C),
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C6'(H6'A,H6'B,H6'C), C7'(H7'A,H7'B,H7'C),
  C8'(H8'A,H8'B,H8'C), C9'(H9'A,H9'B,H9'C), C10'(H10D,H10E,H10F)
;
_shelx_res_checksum              99344
_shelx_hkl_checksum              34041
_olex2_submission_special_instructions 'No special instructions were received'