Kinetics of the <i>Trans</i> Effect in Ruthenium Complexes Provide Insight into the Factors That Control Activity and Stability in CO<sub>2</sub> Electroreduction.
Gonell, Sergio; Assaf, Eric A.; Duffee, Kyle D.; Schauer, Cynthia K.; Miller, Alexander J. M.; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c02912

data_4134905
_publ_section_title
;
 Kinetics of the <i>Trans</i> Effect in Ruthenium Complexes Provide
 Insight into the Factors That Control Activity and Stability in
 CO<sub>2</sub> Electroreduction.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c02912
_journal_year                    2020
_chemical_formula_moiety         'C31 H29.35 N6 O Ru, 2(F6 P), C H2 Cl2'
_chemical_formula_sum            'C32 H31.35 Cl2 F12 N6 O P2 Ru'
_chemical_formula_weight         977.89
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2019-06-18
_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                   17.6809(3)
_cell_length_b                   13.9926(2)
_cell_length_c                   30.1337(5)
_cell_measurement_reflns_used    9986
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      71.998
_cell_measurement_theta_min      2.933
_cell_volume                     7455.1(2)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0508
_diffrn_reflns_av_unetI/netI     0.0258
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            77244
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.262
_diffrn_reflns_theta_min         2.933
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    6.434
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.5316
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1050 before and 0.0525 after correction. The Ratio of minimum to maximum transmission is 0.7054. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.743
_exptl_crystal_description       needle
_exptl_crystal_F_000             3915
_exptl_crystal_size_max          0.276
_exptl_crystal_size_mid          0.119
_exptl_crystal_size_min          0.115
_refine_diff_density_max         0.828
_refine_diff_density_min         -0.586
_refine_diff_density_rms         0.103
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.206
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     622
_refine_ls_number_reflns         7350
_refine_ls_number_restraints     38
_refine_ls_restrained_S_all      1.203
_refine_ls_R_factor_all          0.0842
_refine_ls_R_factor_gt           0.0698
_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^)+66.9841P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1434
_refine_ls_wR_factor_ref         0.1487
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5909
_reflns_number_total             7350
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c02912_si_004.cif
_cod_data_source_block           x1805002
_cod_database_code               4134905
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.525
_shelx_estimated_absorpt_t_min   0.270
_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, All O(H) groups
2. Restrained distances
 O1-H1
 0.87 with sigma of 0.01
 Ru1-H1
 2.700671 with sigma of 0.02
3. Rigid bond restraints
4. Uiso/Uaniso restraints and constraints
Uanis(C30) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(P2) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(F15) \\sim Ueq, Uanis(C30) \\sim Ueq: with sigma of 0 and sigma for
terminal atoms of 0.2
Uanis(F15) \\sim Ueq: with sigma of 0 and sigma for terminal atoms of 0.2
Uanis(F6) \\sim Ueq, Uanis(F10) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(F21) \\sim Ueq: with sigma of 0 and sigma for terminal atoms of 0.2
5. Others
 Sof(F3)=Sof(F6)=Sof(F10)=Sof(F8)=1-FVAR(1)
 Sof(F9)=Sof(F4)=Sof(F5)=Sof(F7)=FVAR(1)
 Sof(P2)=Sof(F12)=Sof(F21)=Sof(F17)=Sof(F15)=Sof(F19)=Sof(F14)=1-FVAR(2)
 Sof(P3)=Sof(F16)=Sof(F20)=Sof(F18)=Sof(F22)=Sof(F13)=Sof(F11)=FVAR(2)
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=1-FVAR(3)
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C34(H34A,H34B), C31(H31A,H31B), C30(H30A,H30B)
6.b Aromatic/amide H refined with riding coordinates:
 C26(H26), C11(H11), C6(H6), C13(H13), C14(H14), C4(H4), C29(H29), C12(H12),
 C27(H27), C5(H5), C15(H15), C23(H23), C16(H16), C21(H21), C18(H18), C7(H7),
 C17(H17), C22(H22), C28(H28)
6.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C)
;
_olex2_submission_special_instructions 'No special instructions were received'