A Highly Efficient Base-Metal Catalyst: Chemoselective Reduction of Imines to Amines Using An Abnormal-NHC‒Fe(0) Complex
Bhunia, Mrinal; Hota, Pradip Kumar; Vijaykumar, Gonela; Adhikari, Debashis; Mandal, Swadhin K.; Organometallics 35 (2016) 2930–; doi:10.1021/acs.organomet.6b00478

data_4088826
_publ_section_title
;
 A Highly Efficient Base-Metal Catalyst: Chemoselective Reduction of
 Imines to Amines Using An Abnormal-NHC--Fe(0) Complex
;
_journal_issue                   17
_journal_name_full               Organometallics
_journal_page_first              2930
_journal_paper_doi               10.1021/acs.organomet.6b00478
_journal_volume                  35
_journal_year                    2016
_chemical_formula_moiety         'C43 H44 Fe N2 O4'
_chemical_formula_sum            'C43 H44 Fe N2 O4'
_chemical_formula_weight         708.65
_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     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-04-21
_audit_creation_method
;
  Olex2 1.2-ac2
  (compiled Nov  7 2012 10:34:12, GUI svn.r4372)
;
_cell_angle_alpha                77.341(8)
_cell_angle_beta                 80.516(7)
_cell_angle_gamma                79.342(7)
_cell_formula_units_Z            2
_cell_length_a                   10.1393(8)
_cell_length_b                   10.7878(10)
_cell_length_c                   18.1314(15)
_cell_measurement_reflns_used    3897
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      24.9890
_cell_measurement_theta_min      2.0460
_cell_volume                     1885.6(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33c (release 11-04-2014 CrysAlis171 .NET)
(compiled Apr 11 2014,15:12:41)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33c (release 11-04-2014 CrysAlis171 .NET)
(compiled Apr 11 2014,15:12:41)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33c (release 11-04-2014 CrysAlis171 .NET)
(compiled Apr 11 2014,15:12:41)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
olex2.solve (L.J. Bourhis, O.V. Dolomanov, R.J. Gildea, J.A.K. Howard,
H. Puschmann, in preparation, 2011)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9580
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.8618
_diffrn_measured_fraction_theta_max 0.9978
_diffrn_measurement_details
;
  1 omega   -5.00  108.00   1.0000   40.8000
omega____ theta____ kappa____ phi______ frames
    -       27.3512   77.0000  -30.0000 113

  2 omega   57.00  107.00   1.0000   40.8000
omega____ theta____ kappa____ phi______ frames
    -       27.3512   77.0000   90.0000 50

  3 omega   18.00   61.00   1.0000   40.8000
omega____ theta____ kappa____ phi______ frames
    -       27.3512  -57.0000  -30.0000 43

  4 omega   35.00  120.00   1.0000   40.8000
omega____ theta____ kappa____ phi______ frames
    -       27.3512  178.0000 -180.0000 85

  5 omega  -52.00   26.00   1.0000   40.8000
omega____ theta____ kappa____ phi______ frames
    -       27.3512  -38.0000 -150.0000 78

  6 omega  -20.00   80.00   1.0000   40.8000
omega____ theta____ kappa____ phi______ frames
    -       27.3512  -99.0000 -180.0000 100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0380216000
_diffrn_orient_matrix_UB_12      -0.0472470000
_diffrn_orient_matrix_UB_13      -0.0029996000
_diffrn_orient_matrix_UB_21      0.0603343000
_diffrn_orient_matrix_UB_22      -0.0380787000
_diffrn_orient_matrix_UB_23      -0.0133143000
_diffrn_orient_matrix_UB_31      0.0082274000
_diffrn_orient_matrix_UB_32      -0.0311480000
_diffrn_orient_matrix_UB_33      0.0380626000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0402
_diffrn_reflns_av_unetI/netI     0.0743
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            11853
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         25.03
_diffrn_reflns_theta_min         1.96
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.443
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86402
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33c (release 11-04-2014 CrysAlis171 .NET)
(compiled Apr 11 2014,15:12:41)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.248
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             748
_exptl_crystal_size_max          0.46
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.001
_refine_diff_density_min         -1.207
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     441
_refine_ls_number_reflns         6654
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0823
_refine_ls_R_factor_gt           0.0618
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0465P)^2^+3.2203P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1331
_refine_ls_wR_factor_ref         0.1461
_reflns_number_gt                5162
_reflns_number_total             6654
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            om6b00478_si_003.cif
_cod_data_source_block           gbfe
_cod_database_code               4088826
_chemical_oxdiff_formula         'C H N2 O4 Fe1'
_reflns_odcompleteness_completeness 86.18
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H9 of C9, H21 of C21, H16 of C16, H36 of C36, H25 of C25, H29 of C29, H14
  of C14, H34 of C34, H32 of C32, H15 of C15, H18 of C18, H27 of C27, H7 of C7,
  H10 of C10, H33 of C33, H26 of C26, H39 of C39, H8 of C8, H11 of C11, H28 of
  C28
 At 1.5 times of:
  {H37A,H37B,H37C} of C37, {H20A,H20B,H20C} of C20, {H38A,H38B,H38C} of C38,
  {H19A,H19B,H19C} of C19, {H40A,H40B,H40C} of C40, {H23A,H23B,H23C} of C23,
  {H41A,H41B,H41C} of C41, {H22A,H22B,H22C} of C22
2. Uiso/Uaniso restraints and constraints
Uanis(O4) = Uanis(O3) = Uanis(O2) = Uanis(O1)
3.a Ternary CH refined with riding coordinates:
 C36(H36), C21(H21), C18(H18), C39(H39)
3.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C29(H29), C9(H9), C34(H34), C16(H16), C25(H25), C32(H32), C15(H15),
 C10(H10), C33(H33), C7(H7), C27(H27), C8(H8), C11(H11), C28(H28), C26(H26)
3.c Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C), C19(H19A,H19B,H19C), C40(H40A,H40B,H40C), C23(H23A,H23B,
 H23C), C41(H41A,H41B,H41C), C22(H22A,H22B,H22C), C20(H20A,H20B,H20C), C38(H38A,
 H38B,H38C)
;