Enhanced Hydride Donation Achieved Molybdenum Catalyzed Direct N-Alkylation of Anilines or Nitroarenes with Alcohols: From Computational Design to Experiment
Li, Weikang; Huang, Ming; Liu, Jiahao; Huang, Yong-Liang; Lan, Xiao-Bing; Ye, Zongren; Zhao, Cunyuan; Liu, Yan; Ke, Zhuofeng; ACS Catalysis 11 (2021) 10377–10382; doi:10.1021/acscatal.1c02956

data_4518989
_publ_section_title
;
 Enhanced Hydride Donation Achieved Molybdenum Catalyzed Direct
 N-Alkylation of Anilines or Nitroarenes with Alcohols: From Computational
 Design to Experiment
;
_journal_issue                   16
_journal_name_full               'ACS Catalysis'
_journal_page_first              10377
_journal_page_last               10382
_journal_paper_doi               10.1021/acscatal.1c02956
_journal_volume                  11
_journal_year                    2021
_chemical_formula_moiety         'C14 H11 Mo N3 O4'
_chemical_formula_sum            'C14 H11 Mo N3 O4'
_chemical_formula_weight         381.20
_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
_audit_creation_date             2021-04-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                79.028(9)
_cell_angle_beta                 81.338(10)
_cell_angle_gamma                63.090(14)
_cell_formula_units_Z            2
_cell_length_a                   8.4036(13)
_cell_length_b                   8.9796(11)
_cell_length_c                   11.1670(10)
_cell_measurement_reflns_used    2273
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      75.3590
_cell_measurement_theta_min      4.0370
_cell_volume                     735.69(18)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2913
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.961
_diffrn_measured_fraction_theta_max 0.961
_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   -105.00  -1.00   1.00    4.00    --  -41.39 -19.00-150.00  104
  2  \w    -66.00  -2.00   1.00    4.00    --  -41.39 125.00 -30.00   64
  3  \w   -115.00 -21.00   1.00    4.00    --  -41.39 -38.00 150.00   94
  4  \w     27.00  67.00   1.00    4.00    --   41.39 -99.00 -60.00   40
  5  \w      4.00  81.00   1.00    4.00    --   41.39 -99.00 120.00   77
  6  \w     98.00 165.00   1.00   16.00    --  112.00 125.00 -60.00   67
  7  \w     82.00 115.00   1.00   16.00    --  112.00-125.00-120.00   33
  8  \w    101.00 173.00   1.00   16.00    --  112.00 125.00   0.00   72
  9  \w     48.00 118.00   1.00   16.00    --  112.00-125.00  60.00   70
 10  \w    146.00 178.00   1.00   16.00    --  112.00  30.00  60.00   32
 11  \w     29.00 103.00   1.00   16.00    --  112.00 -94.00 -60.00   74
 12  \w     90.00 134.00   1.00   16.00    --  112.00  30.00  60.00   44
 13  \w    136.00 178.00   1.00   16.00    --  112.00  45.00  90.00   42
 14  \w     87.00 133.00   1.00   16.00    --  112.00  45.00  90.00   46
 15  \w     36.00  95.00   1.00   16.00    --  112.00 -30.00  60.00   59
 16  \w     41.00 128.00   1.00   16.00    --  112.00 -77.00  30.00   87
 17  \w    100.00 145.00   1.00   16.00    --  112.00 125.00 -30.00   45
 18  \w     65.00 133.00   1.00   16.00    --  112.00 -30.00-120.00   68
 19  \w     93.00 118.00   1.00   20.00    --  112.00-125.00-180.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1420752000
_diffrn_orient_matrix_UB_12      0.0627360000
_diffrn_orient_matrix_UB_13      0.0031913000
_diffrn_orient_matrix_UB_21      -0.1478606000
_diffrn_orient_matrix_UB_22      0.1678450000
_diffrn_orient_matrix_UB_23      0.0369851000
_diffrn_orient_matrix_UB_31      0.0211740000
_diffrn_orient_matrix_UB_32      -0.0750488000
_diffrn_orient_matrix_UB_33      0.1359272000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0947
_diffrn_reflns_av_unetI/netI     0.0923
_diffrn_reflns_Laue_measured_fraction_full 0.961
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            4060
_diffrn_reflns_point_group_measured_fraction_full 0.961
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        64.484
_diffrn_reflns_theta_max         64.484
_diffrn_reflns_theta_min         4.043
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.503
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45556
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.721
_exptl_crystal_description       block
_exptl_crystal_F_000             380
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.08
_refine_diff_density_max         2.279
_refine_diff_density_min         -0.908
_refine_diff_density_rms         0.242
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     179
_refine_ls_number_reflns         2385
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.093
_refine_ls_R_factor_all          0.1170
_refine_ls_R_factor_gt           0.1079
_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^)+(0.1863P)^2^+2.9448P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2775
_refine_ls_wR_factor_ref         0.2885
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2084
_reflns_number_total             2385
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c02956_si_004.cif
_cod_data_source_block           a20082006a0826
_cod_database_code               4518989
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHONMo
_chemical_oxdiff_usercomment     mo-py-c-nhc
_shelx_estimated_absorpt_t_max   0.585
_shelx_estimated_absorpt_t_min   0.399
_reflns_odcompleteness_completeness 99.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Others
 Fixed Uiso: H6(0.1) H7(0.088) H14(0.086) H11(0.085) H12(0.108) H13(0.102)
 H9A(0.084) H9B(0.084) H8A(0.125) H8B(0.125) H8C(0.125)
 Fixed X: H6(0.69185) H7(0.450072) H14(0.320043) H11(0.052622) H12(-0.122965)
 H13(0.010742) H9A(0.335364) H9B(0.479697) H8A(0.963551) H8B(0.948071)
 H8C(0.837074)
 Fixed Y: H6(1.155129) H7(1.253878) H14(0.56904) H11(1.114409) H12(0.984369)
 H13(0.711685) H9A(1.11097) H9B(0.935116) H8A(0.704904) H8B(0.862443)
 H8C(0.765375)
 Fixed Z: H6(-0.00282) H7(0.165904) H14(0.260979) H11(0.357962) H12(0.335759)
 H13(0.287268) H9A(0.347541) H9B(0.401171) H8A(0.053502) H8B(-0.042066) H8C(-
 0.05322)
;
_shelx_res_checksum              86128
_shelx_hkl_checksum              35360
_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 1.877
_oxdiff_exptl_absorpt_empirical_full_min 0.349