Efficient and phosphine-free bidentate N-heterocyclic carbene/ruthenium catalytic systems for the dehydrogenative amidation of alcohols and amines
Wu, Xuan-Jun; Wang, Hua-Jing; Yang, Zhao-Qi; Tang, Xiao-Sheng; Yuan, Ye; Su, Wei; Chen, Cheng; Verpoort, Francis; Organic Chemistry Frontiers 6 (2019) 563–; doi:10.1039/C8QO00902C

data_1554449
_publ_section_title
;
 Efficient and phosphine-free bidentate N-heterocyclic carbene/ruthenium
 catalytic systems for the dehydrogenative amidation of alcohols and
 amines
;
_journal_issue                   5
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              563
_journal_paper_doi               10.1039/C8QO00902C
_journal_volume                  6
_journal_year                    2019
_chemical_formula_moiety         'C30 H37 I N2 Ru'
_chemical_formula_sum            'C30 H37 I N2 Ru'
_chemical_formula_weight         653.58
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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
_audit_creation_date             2018-06-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_audit_update_record
;
2018-06-13 deposited with the CCDC.
2018-11-16 downloaded from the CCDC.
;
_cell_angle_alpha                89.442(3)
_cell_angle_beta                 89.312(2)
_cell_angle_gamma                88.419(3)
_cell_formula_units_Z            4
_cell_length_a                   12.2395(19)
_cell_length_b                   14.363(2)
_cell_length_c                   18.399(3)
_cell_measurement_reflns_used    5089
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      24.87
_cell_measurement_theta_min      2.22
_cell_volume                     3232.9(9)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0455
_diffrn_reflns_av_unetI/netI     0.0726
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            22547
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.107
_exptl_absorpt_coefficient_mu    1.457
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.343
_exptl_crystal_description       plate
_exptl_crystal_F_000             1312
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: chloroform/Pentane'
_refine_diff_density_max         1.175
_refine_diff_density_min         -0.940
_refine_diff_density_rms         0.194
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.002
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     629
_refine_ls_number_reflns         11250
_refine_ls_number_restraints     364
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0941
_refine_ls_R_factor_gt           0.0641
_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^)+(0.1428P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1851
_refine_ls_wR_factor_ref         0.2175
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7635
_reflns_number_total             11250
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8qo00902c2.cif
_cod_data_source_block           2
_cod_database_code               1554449
_shelx_shelxl_version_number     2014/7
_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
2. Rigid bond restraints
 C4BA, C8FA
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C12) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C20)
\\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C11) \\sim Ueq,
Uanis(C5) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C28)
\\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C2BA) \\sim Ueq, Uanis(C7DA) \\sim Ueq,
Uanis(C6) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C9)
\\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C5CA) \\sim Ueq,
Uanis(C14) \\sim Ueq, Uanis(C7CA) \\sim Ueq, Uanis(C8CA) \\sim Ueq, Uanis(C9CA)
\\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C2DA) \\sim Ueq, Uanis(C4DA) \\sim Ueq,
Uanis(C9EA) \\sim Ueq, Uanis(C1FA) \\sim Ueq, Uanis(C2FA) \\sim Ueq,
Uanis(C3FA) \\sim Ueq, Uanis(C4FA) \\sim Ueq, Uanis(C5FA) \\sim Ueq,
Uanis(C6FA) \\sim Ueq, Uanis(C7FA) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C22)
\\sim Ueq, Uanis(C1EA) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C30) \\sim Ueq,
Uanis(C4EA) \\sim Ueq, Uanis(C5EA) \\sim Ueq, Uanis(C6EA) \\sim Ueq,
Uanis(C7EA) \\sim Ueq, Uanis(C8EA) \\sim Ueq, Uanis(C0FA) \\sim Ueq, Uanis(C7)
\\sim Ueq, Uanis(C3AA) \\sim Ueq, Uanis(C4AA) \\sim Ueq, Uanis(C24) \\sim Ueq,
Uanis(C1BA) \\sim Ueq, Uanis(C4BA) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C8)
\\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C6BA) \\sim Ueq, Uanis(C3BA) \\sim Ueq,
Uanis(C1DA) \\sim Ueq, Uanis(C8FA) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
4.a Ternary CH refined with riding coordinates:
 C20(H20), C7CA(H7CA), C9CA(H9CA), C24(H24), C6BA(H6BA)
4.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C4BA(H4BA,H4BB)
4.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C5(H5), C28(H28), C31(H31), C13(H13), C9(H9), C18(H18), C27(H27),
 C2DA(H2DA), C4DA(H4DA), C1FA(H1FA), C2FA(H2FA), C3FA(H3FA), C1EA(H1EA),
 C6EA(H6EA), C7EA(H7EA), C0FA(H0FA)
4.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C6FA(H6FA,H6FB,H6FC), C17(H17A,H17B,H17C), C22(H22A,H22B,
 H22C), C21(H21A,H21B,H21C), C30(H30A,H30B,H30C), C4EA(H4EA,H4EB,H4EC),
 C5EA(H5EA,H5EB,H5EC), C4AA(H4AA,H4AB,H4AC), C1BA(H1BA,H1BB,H1BC), C23(H23A,
 H23B,H23C), C8(H8A,H8B,H8C), C25(H25A,H25B,H25C), C3BA(H3BA,H3BB,H3BC),
 C1DA(H1DA,H1DB,H1DC), C8FA(H8FA,H8FB,H8FC)
;
_olex2_submission_special_instructions 'No special instructions were received'