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_4514656
_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_absolute_configuration ad
_chemical_formula_moiety         'C24 H42 Cl N2 P Ru, 0.5(C6 H12)'
_chemical_formula_sum            'C27 H48 Cl N2 P Ru'
_chemical_formula_weight         568.16
_space_group_crystal_system      tetragonal
_space_group_IT_number           76
_space_group_name_Hall           'P 4w'
_space_group_name_H-M_alt        'P 41'
_symmetry_space_group_name_Hall  'P 4w'
_symmetry_space_group_name_H-M   'P 41'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-08-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   13.2477(9)
_cell_length_b                   13.2477(9)
_cell_length_c                   32.623(2)
_cell_measurement_reflns_used    8134
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.13
_cell_measurement_theta_min      2.87
_cell_volume                     5725.4(7)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2013.6-2 (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'XM (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_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  0.0518
_diffrn_reflns_av_unetI/netI     0.0598
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            25821
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.280
_diffrn_reflns_theta_min         1.873
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.714
_exptl_absorpt_correction_T_max  0.0656
_exptl_absorpt_correction_T_min  0.0389
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1427 before and 0.0629 after correction.
The Ratio of minimum to maximum transmission is 0.5930.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.318
_exptl_crystal_description       plate
_exptl_crystal_F_000             2400
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.29
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.336
_refine_diff_density_min         -0.354
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Flack x determined using 2573 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     604
_refine_ls_number_reflns         9983
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0319
_refine_ls_R_factor_gt           0.0309
_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^)+(0.0179P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0690
_refine_ls_wR_factor_ref         0.0697
_reflns_Friedel_coverage         0.967
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                9769
_reflns_number_total             9983
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b04345_si_003.cif
_cod_data_source_block           Complex3
_cod_original_cell_volume        5725.4(9)
_cod_database_code               4514656
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.804
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6355(11)
 0.3645(11)
2. 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
3.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C36(H36), C39(H39)
3.b Secondary CH2 refined with riding coordinates:
 C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B), C52(H52A,H52B), C53(H53A,
 H53B), C54(H54A,H54B)
3.c Aromatic/amide H refined with riding coordinates:
 C18(H18), C43(H43)
3.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C16(H16A,H16B,H16C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C24(H24A,H24B,H24C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,
 H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C),
 C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C40(H40A,H40B,H40C), C44(H44A,H44B,
 H44C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C)
;
_shelx_res_checksum              45080
_shelx_hkl_checksum              74488
_olex2_submission_special_instructions 'No special instructions were received'