Aerobic dehydrogenation of amines to nitriles catalyzed by triazolylidene ruthenium complexes with O<sub>2</sub> as terminal oxidant.
Olivares, Marta; Knörr, Pascal; Albrecht, Martin; Dalton transactions (Cambridge, England : 2003) 49 (2020) 1981–1991; doi:10.1039/c9dt04873a

data_7703332
_publ_section_title
;
 Aerobic dehydrogenation of amines to nitriles catalyzed by triazolylidene
 ruthenium complexes with O<sub>2</sub> as terminal oxidant.
;
_journal_issue                   6
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              1981
_journal_page_last               1991
_journal_paper_doi               10.1039/c9dt04873a
_journal_volume                  49
_journal_year                    2020
_chemical_formula_moiety         '2(C20 H26 Cl N4 O Ru), 2(C F3 O3 S), O'
_chemical_formula_sum            'C42 H52 Cl2 F6 N8 O9 Ru2 S2'
_chemical_formula_weight         1264.07
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_audit_update_record
;
2019-10-10 deposited with the CCDC.	2020-01-21 downloaded from the CCDC.
;
_cell_angle_alpha                106.164(5)
_cell_angle_beta                 98.769(4)
_cell_angle_gamma                116.609(3)
_cell_formula_units_Z            2
_cell_length_a                   13.3854(4)
_cell_length_b                   14.8258(5)
_cell_length_c                   16.1157(12)
_cell_measurement_reflns_used    12083
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      27.4340
_cell_measurement_theta_min      1.6930
_cell_volume                     2599.4(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0965
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.940
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -95.00 -34.00   1.00   15.00    --    0.00 178.00-180.00   61
  2  \w    -38.00  76.00   1.00   15.00    --    0.00  57.00   0.00  114
  3  \w    -20.00  82.00   1.00   32.50    --   27.42 -99.00 -60.00  102
  4  \w    -10.00 103.00   1.00   32.50    --   27.42  57.00  60.00  113
  5  \w    -28.00 109.00   1.00   32.50    --   27.42  38.00  30.00  137
  6  \w    -28.00 109.00   1.00   32.50    --   27.42  38.00 -60.00  137
  7  \w    -49.00  65.00   1.00   32.50    --   27.42 -57.00 150.00  114
  8  \w     35.00 122.00   1.00   32.50    --   27.42 178.00-150.00   87
  9  \w    -36.00   7.00   1.00   32.50    --   27.42 114.00-114.79   43
 10  \w    -38.00  76.00   1.00   15.00    --    0.00  57.00 -30.00  114
 11  \w    -49.00  65.00   1.00   32.50    --   27.42 -57.00   0.00  114
 12  \w    -49.00 -11.00   1.00   32.50    --   27.42 -57.00 -90.00   38
 13  \w    -10.00 103.00   1.00   32.50    --   27.42  57.00 150.00  113
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0352489000
_diffrn_orient_matrix_UB_12      -0.0400533000
_diffrn_orient_matrix_UB_13      0.0153679000
_diffrn_orient_matrix_UB_21      -0.0251070000
_diffrn_orient_matrix_UB_22      -0.0404311000
_diffrn_orient_matrix_UB_23      -0.0451051000
_diffrn_orient_matrix_UB_31      0.0452573000
_diffrn_orient_matrix_UB_32      -0.0120487000
_diffrn_orient_matrix_UB_33      0.0085646000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0828
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.940
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            14470
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.940
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.190
_diffrn_reflns_theta_min         1.670
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.844
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71832
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.43c (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.615
_exptl_crystal_description       plate
_exptl_crystal_F_000             1280
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.02
_refine_diff_density_max         2.334
_refine_diff_density_min         -1.341
_refine_diff_density_rms         0.142
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     633
_refine_ls_number_reflns         14470
_refine_ls_number_restraints     28
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.1048
_refine_ls_R_factor_gt           0.0706
_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^)+(0.1154P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1834
_refine_ls_wR_factor_ref         0.1956
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9449
_reflns_number_total             14470
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt04873a2.cif
_cod_data_source_block           complex6a_18MA036_PK21
_cod_depositor_comments
'Adding full bibliography for 7703329--7703332.cif.'
_cod_original_cell_volume        2599.4(2)
_cod_database_code               7703332
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C21H26Cl1F3N4O4Ru1S1
_chemical_oxdiff_usercomment     PK21
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.849
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6929(12)
 0.3071(12)
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. Restrained distances
 S1-C52
 1.85 with sigma of 0.02
 F2-C52 \\sim F1-C52 \\sim F3-C52
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C52) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F1) \\sim
Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C24) = Uanis(C25)
Uanis(O4) = Uanis(O3) = Uanis(O2)
5.a Ternary CH refined with riding coordinates:
 C48(H48), C23(H23)
5.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C39(H39A,H39B)
5.c Aromatic/amide H refined with riding coordinates:
 C30(H30), C27(H27), C2(H2), C29(H29), C46(H46), C21(H21), C22(H22), C5(H5),
 C4(H4), C19(H19), C18(H18), C47(H47), C28(H28), C44(H44), C3(H3), C43(H43)
5.d Idealised Me refined as rotating group:
 C49(H49A,H49B,H49C), C12(H12A,H12B,H12C), C25(H25A,H25B,H25C), C24(H24A,H24B,
 H24C), C37(H37A,H37B,H37C), C50(H50A,H50B,H50C), C16(H16A,H16B,H16C), C15(H15A,
 H15B,H15C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C)
;
_shelx_res_checksum              4040
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.536
_oxdiff_exptl_absorpt_empirical_full_min 0.657
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
_twin_special_details
;
Component 2 rotated by -179.9618\% 
 around [0.00 0.90 -0.43] (reciprocal) or [0.45 0.90 -0.00] (direct)
;