Iridium-(κ2-NSi) Catalyzed Dehydrogenation of Formic Acid: Effect of Auxiliary Ligands on the Catalytic Performance
Gomez-España, Alejandra; Lopez-Morales, Jorge L; Español-Sanchez, Belinda; García-Orduña, Pilar; Lahoz, Fernando J.; Iglesias, Manuel; Fernandez-Alvarez, Francisco J; Dalton Transactions  (2023) –; doi:10.1039/D3DT00744H

data_7712877
_publ_section_title
;
 Iridium-(\k2-NSi) Catalyzed Dehydrogenation of Formic Acid: Effect of
 Auxiliary Ligands on the Catalytic Performance
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00744H
_journal_year                    2023
_chemical_formula_moiety         'C27 H37 F3 Ir N3 O4 S Si, C7 H8'
_chemical_formula_sum            'C34 H45 F3 Ir N3 O4 S Si'
_chemical_formula_weight         869.08
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-09-09
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-03-08 deposited with the CCDC.	2023-04-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.561(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.8989(6)
_cell_length_b                   19.4839(7)
_cell_length_c                   11.8251(4)
_cell_measurement_reflns_used    9735
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      34.145
_cell_measurement_theta_min      2.780
_cell_volume                     3661.7(2)
_computing_cell_refinement       'SAINT V8.40B (Bruker AXS, 2016) in APEX4 '
_computing_data_collection       'SAINT V8.40B (Bruker AXS, 2016) in APEX4'
_computing_data_reduction        'SAINT V8.40B (Bruker AXS, 2016) in APEX4'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'XS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Pilatus 6M-Dectris'
_diffrn_detector_type            'Pilatus 6M-Dectris area detector'
_diffrn_measured_fraction_theta_full 0.941
_diffrn_measured_fraction_theta_max 0.803
_diffrn_measurement_device       'Dectris area detector and MD2M diffractometer'
_diffrn_measurement_device_type  'Dectris area detector and MD2M diffractometer'
_diffrn_measurement_method       'phi rotation'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.7294
_diffrn_reflns_av_R_equivalents  0.0781
_diffrn_reflns_av_unetI/netI     0.0608
_diffrn_reflns_Laue_measured_fraction_full 0.941
_diffrn_reflns_Laue_measured_fraction_max 0.803
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            53433
_diffrn_reflns_point_group_measured_fraction_full 0.941
_diffrn_reflns_point_group_measured_fraction_max 0.803
_diffrn_reflns_theta_full        27.500
_diffrn_reflns_theta_max         34.091
_diffrn_reflns_theta_min         1.315
_diffrn_source                   synchrotron
_diffrn_source_type              'BL13-XALOC beamline,ALBA'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.032
_exptl_absorpt_correction_T_max  0.2709
_exptl_absorpt_correction_T_min  0.1248
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.2183 before and 0.1053 after correction.
The Ratio of minimum to maximum transmission is 0.4607.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.576
_exptl_crystal_description       needle
_exptl_crystal_F_000             1744
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene / pentane'
_exptl_crystal_size_max          0.060
_exptl_crystal_size_mid          0.020
_exptl_crystal_size_min          0.005
_refine_diff_density_max         6.905
_refine_diff_density_min         -2.744
_refine_diff_density_rms         0.301
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     438
_refine_ls_number_reflns         11179
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0693
_refine_ls_R_factor_gt           0.0595
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1175P)^2^+6.9568P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1654
_refine_ls_wR_factor_ref         0.1756
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9705
_reflns_number_total             11179
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00744h2.cif
_cod_data_source_block           cmpnd_3
_cod_database_code               7712877
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.824
_shelx_estimated_absorpt_t_min   0.196
_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.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C15(H15), C16(H16), C18(H18), C22(H22), C24(H24),
 C25(H25), C52(H52), C53(H53), C55(H55), C56(H56), C57(H57)
2.b Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C20(H20A,H20B,
 H20C), C26(H26A,H26B,H26C), C58(H58A,H58B,H58C)
;
_shelx_res_checksum              84400
_shelx_hkl_checksum              61651
_olex2_submission_special_instructions 'No special instructions were received'