DBU as base and ligand in phosphine-free ruthenium complexes for hydrogenation of CO<sub>2</sub>.
Preston, Andrew Z.; Phearman, Alexander S.; Quiroz, Manuel; Flowers, Sarah E.; Devi, Nilakshi; Zall, Christopher M.; Wiedner, Eric S.; Appel, Aaron M.; Linehan, John C.; Chemical communications (Cambridge, England) 61 (2025) 11247–11250; doi:10.1039/d5cc00512d

data_7134741
_publ_section_title
;
 DBU as base and ligand in phosphine-free ruthenium complexes for
 hydrogenation of CO<sub>2</sub>.
;
_journal_issue                   60
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              11247
_journal_page_last               11250
_journal_paper_doi               10.1039/d5cc00512d
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C23 H37 N4 Ru, F6 P, C4 H10 O'
_chemical_formula_sum            'C27 H47 F6 N4 O P Ru'
_chemical_formula_weight         689.72
_chemical_name_systematic        '[Cp*Ru(DBU)(NCCH3)2][PF6]'
_chemical_properties_physical    Air-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yac'
_space_group_name_H-M_alt        'P 1 2/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-12-28
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-01-29 deposited with the CCDC.	2025-06-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.738(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1425(7)
_cell_length_b                   10.9767(6)
_cell_length_c                   24.5384(13)
_cell_measurement_reflns_used    9757
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.895
_cell_measurement_theta_min      2.518
_cell_volume                     3223.5(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_detector                 'Bruker KAPPA APEX III CCD'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-III CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'TRIUMPH monochromator'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0522
_diffrn_reflns_av_unetI/netI     0.0290
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            71055
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.952
_diffrn_reflns_theta_min         2.022
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_type              'Incoatec I\ms 3.0'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.597
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6443
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016) was used for absorption correction.
wR2(int) was 0.0694 before and 0.0559 after correction.
The Ratio of minimum to maximum transmission is 0.8641.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.421
_exptl_crystal_description       plate
_exptl_crystal_F_000             1432
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Acetonitrile/DBU/diethylether'
_exptl_crystal_size_max          0.219
_exptl_crystal_size_mid          0.159
_exptl_crystal_size_min          0.112
_refine_diff_density_max         1.513
_refine_diff_density_min         -0.907
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.191
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     471
_refine_ls_number_reflns         7710
_refine_ls_number_restraints     166
_refine_ls_restrained_S_all      1.205
_refine_ls_R_factor_all          0.0738
_refine_ls_R_factor_gt           0.0570
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0263P)^2^+11.5191P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1237
_refine_ls_wR_factor_ref         0.1348
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6379
_reflns_number_total             7710
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc00512d2.cif
_cod_data_source_block           asp_iv_17_c
_cod_depositor_comments          'Adding full bibliography for 7134741.cif.'
_cod_database_code               7134741
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.936
_shelx_estimated_absorpt_t_min   0.880
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Ru1-C15A \\sim Ru1-C15B
 with sigma of 0.04
 C16A-C21A \\sim C16B-C21B
 with sigma of 0.04
 Ru1-C19A \\sim Ru1-C19B
 with sigma of 0.04
 C16A-C22A \\sim C16B-C22B
 with sigma of 0.04
 Ru1-C21A \\sim Ru1-C21B
 with sigma of 0.04
 C16A-C20A \\sim C16B-C20B
 with sigma of 0.04
 Ru1-C16A \\sim Ru1-C16B
 with sigma of 0.04
 Ru1-C17A \\sim Ru1-C17B
 with sigma of 0.04
 Ru1-C14A \\sim Ru1-C14B
 with sigma of 0.04
 C15A-C16A \\sim C15B-C16B
 with sigma of 0.04
 C15A-C19A \\sim C15B-C19B
 with sigma of 0.04
 C17A-C16A \\sim C17B-C16B
 with sigma of 0.04
 C14A-C16A \\sim C14B-C16B
 with sigma of 0.04
 Ru1-C23A \\sim Ru1-C23B
 with sigma of 0.04
 C16A-C18A \\sim C16B-C18B
 with sigma of 0.04
 Ru1-C18A \\sim Ru1-C18B
 with sigma of 0.04
 C15A-C21A \\sim C15B-C21B
 with sigma of 0.04
 C15A-C17A \\sim C15B-C17B
 with sigma of 0.04
 Ru1-C22A \\sim Ru1-C22B
 with sigma of 0.04
 C15A-C14A \\sim C15B-C14B
 with sigma of 0.04
 C17A-C21A \\sim C17B-C21B
 with sigma of 0.04
 C17A-C23A \\sim C17B-C23B
 with sigma of 0.04
 C17A-C22A \\sim C17B-C22B
 with sigma of 0.04
 C15A-C18A \\sim C15B-C18B
 with sigma of 0.04
 C14A-C19A \\sim C14B-C19B
 with sigma of 0.04
 C14A-C23A \\sim C14B-C23B
 with sigma of 0.04
 C18A-C19A \\sim C18B-C19B
 with sigma of 0.04
 C18A-C23A \\sim C18B-C23B
 with sigma of 0.04
 C17A-C14A \\sim C17B-C14B
 with sigma of 0.04
 C18A-C22A \\sim C18B-C22B
 with sigma of 0.04
 C17A-C18A \\sim C17B-C18B
 with sigma of 0.04
 C15A-C20A \\sim C15B-C20B
 with sigma of 0.04
 C14A-C20A \\sim C14B-C20B
 with sigma of 0.04
 C19A-C23A \\sim C19B-C23B
 with sigma of 0.04
 C14A-C18A \\sim C14B-C18B
 with sigma of 0.04
 C21A-C22A \\sim C21B-C22B
 with sigma of 0.04
 C23A-C22A \\sim C23B-C22B
 with sigma of 0.04
 Ru1-C20A \\sim Ru1-C20B
 with sigma of 0.04
 C20A-C19A \\sim C20B-C19B
 with sigma of 0.04
 C20A-C21A \\sim C20B-C21B
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(N3) \\sim Ueq, Uanis(C14A) \\sim Ueq, Uanis(C14B) \\sim Ueq, Uanis(C15A)
\\sim Ueq, Uanis(C15B) \\sim Ueq, Uanis(C16A) \\sim Ueq, Uanis(C16B) \\sim Ueq,
Uanis(C17A) \\sim Ueq, Uanis(C17B) \\sim Ueq, Uanis(C18A) \\sim Ueq,
Uanis(C18B) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C20A) \\sim Ueq, Uanis(C20B) \\sim Ueq, Uanis(C21A) \\sim Ueq,
Uanis(C21B) \\sim Ueq, Uanis(C22A) \\sim Ueq, Uanis(C22B) \\sim Ueq,
Uanis(C23A) \\sim Ueq, Uanis(C23B) \\sim Ueq, Uanis(C19A) \\sim Ueq,
Uanis(C19B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F2A) = Uanis(F3A)
Uanis(F2B) = Uanis(F3B)
Uanis(F6) = Uanis(F7)
4. Others
 Sof(C14B)=Sof(C15B)=Sof(C16B)=Sof(C17B)=Sof(C18B)=Sof(C19B)=Sof(H19D)=
 Sof(H19E)=Sof(H19F)=Sof(C20B)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C21B)=
 Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C22B)=Sof(H22D)=Sof(H22E)=Sof(H22F)=
 Sof(C23B)=Sof(H23D)=Sof(H23E)=Sof(H23F)=1-FVAR(1)
 Sof(C14A)=Sof(C15A)=Sof(C16A)=Sof(C17A)=Sof(C18A)=Sof(C19A)=Sof(H19A)=
 Sof(H19B)=Sof(H19C)=Sof(C20A)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C21A)=
 Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22A)=Sof(H22A)=Sof(H22B)=Sof(H22C)=
 Sof(C23A)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(1)
 Sof(F2B)=Sof(F3B)=1-FVAR(2)
 Sof(F2A)=Sof(F3A)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C25(HC,HD), C26(HE,HF), C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B),
 C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B)
5.b Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C19A(H19A,H19B,H19C), C19B(H19D,
 H19E,H19F), C20A(H20A,H20B,H20C), C20B(H20D,H20E,H20F), C21A(H21A,H21B,H21C),
 C21B(H21D,H21E,H21F), C22A(H22A,H22B,H22C), C22B(H22D,H22E,H22F), C23A(H23A,
 H23B,H23C), C23B(H23D,H23E,H23F), C24(H,HA,HB), C27(HG,HH,HI)
;
_shelx_res_checksum              7178
_shelx_hkl_checksum              27897
_olex2_exptl_crystal_mounting_method 'mounted on a Cryoloop using ParaBar oil'
_olex2_submission_original_sample_id ASP_IV_17_C
_olex2_submission_special_instructions 'No special instructions were received'