Iridium and Ruthenium Complexes of N-Heterocyclic Carbene- and Pyridinol-Derived Chelates as Catalysts for Aqueous Carbon Dioxide Hydrogenation and Formic Acid Dehydrogenation: The Role of the Alkali Metal
Siek, Sopheavy; Burks, Dalton B.; Gerlach, Deidra L.; Liang, Guangchao; Tesh, Jamie M.; Thompson, Courtney R.; Qu, Fengrui; Shankwitz, Jennifer E.; Vasquez, Robert M.; Chambers, Nicole; Szulczewski, Gregory J.; Grotjahn, Douglas B.; Webster, Charles Edwin; Papish, Elizabeth T.; Organometallics 36 (2017) 1091–; doi:10.1021/acs.organomet.6b00806

data_4087091
_publ_section_title
;
 Iridium and Ruthenium Complexes of N-Heterocyclic Carbene- and
 Pyridinol-Derived Chelates as Catalysts for Aqueous Carbon Dioxide
 Hydrogenation and Formic Acid Dehydrogenation: The Role of the Alkali
 Metal
;
_journal_issue                   6
_journal_name_full               Organometallics
_journal_page_first              1091
_journal_paper_doi               10.1021/acs.organomet.6b00806
_journal_volume                  36
_journal_year                    2017
_chemical_formula_moiety         'C20 H22 Ag N6 O2, C F3 O3 S'
_chemical_formula_sum            'C21 H22 Ag F3 N6 O5 S'
_chemical_formula_weight         635.37
_chemical_name_common            '7 [Ag(NHC(Me)-py(OMe))2]OTf'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                72.9460(10)
_cell_angle_beta                 77.6720(10)
_cell_angle_gamma                77.6640(10)
_cell_formula_units_Z            2
_cell_length_a                   7.2377(2)
_cell_length_b                   12.3949(4)
_cell_length_c                   14.7323(5)
_cell_measurement_reflns_used    9232
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      34.7076
_cell_measurement_theta_min      2.9310
_cell_volume                     1218.15(7)
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 V2013.10-0 (Bruker, 2013)'
_computing_data_reduction        'SAINT V8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Mercury CSD 3.5.1 (2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      173(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_device_type  'Bruker AXS SMART APEX2 CCD diffractometer'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0154
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            10381
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         34.804
_diffrn_reflns_theta_min         1.741
_diffrn_source                   'sealed X-ray tube'
_exptl_absorpt_coefficient_mu    0.982
_exptl_absorpt_correction_T_max  0.746888
_exptl_absorpt_correction_T_min  0.574779
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'TWINABS (Sheldrick, 2007)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.732
_exptl_crystal_description       rod
_exptl_crystal_F_000             640
_exptl_crystal_size_max          0.400
_exptl_crystal_size_mid          0.270
_exptl_crystal_size_min          0.230
_refine_diff_density_max         0.656
_refine_diff_density_min         -0.593
_refine_diff_density_rms         0.089
_refine_ls_extinction_coef       0.0094(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.108
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     340
_refine_ls_number_reflns         10381
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.108
_refine_ls_R_factor_all          0.0232
_refine_ls_R_factor_gt           0.0216
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0345P)^2^+0.2515P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0623
_refine_ls_wR_factor_ref         0.0636
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9865
_reflns_number_total             10381
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00806_si_003.cif
_cod_data_source_block           complex7_SS10_t5_dg
_cod_depositor_comments
'Adding full bibliography for 4087084--4087091.cif.'
_cod_database_code               4087091
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.695
_shelx_estimated_absorpt_t_max   0.806
_exptl_absorpt_special_details
;
The crystal was found to be non-merohedrally 
twinned. The orientation matrices for the two components were 
identified using the program Cell_Now, with the two components 
being related by a 5 degree rotation around the two axes. The 
two components were integrated using Saint. 56913 reflections 
(9967 unique) involved component 1 only (mean I/sigma = 
33.3), 56407 reflections (9972 unique) involved component 2 
only (mean I/sigma = 19.4), and 3733 reflections (1172 unique) 
involved both components (mean I/sigma = 42.7). The exact 
twin matrix identified by the integration program was found to 
be 0.995 -0.051 -0.021, 0.168 1.037 0.039, 0.023 -0.018 1.000. 

The data were corrected for absorption using twinabs, and 
the structure was solved using direct methods and refined with 
only the non-overlapping reflections of component 1 with a 
resolution better than 0.62 Angstrom.
;
_shelx_res_checksum              20037
_shelx_hkl_checksum              9931