Manganese-Pincer-Catalyzed Nitrile Hydration, α-Deuteration, and α-Deuterated Amide Formation via Metal Ligand Cooperation
Zhou, Quan-Quan; Zou, You-Quan; Kar, Sayan; Diskin-Posner, Yael; Ben-David, Yehoshoa; Milstein, David; ACS Catalysis 11 (2021) 10239–10245; doi:10.1021/acscatal.1c01748

data_4518980
_publ_section_title
;
 Manganese-Pincer-Catalyzed Nitrile Hydration, \a-Deuteration, and
 \a-Deuterated Amide Formation via Metal Ligand Cooperation
;
_journal_issue                   16
_journal_name_full               'ACS Catalysis'
_journal_page_first              10239
_journal_page_last               10245
_journal_paper_doi               10.1021/acscatal.1c01748
_journal_volume                  11
_journal_year                    2021
_chemical_formula_moiety         'C32 H46 F Mn N2 O2 P2'
_chemical_formula_sum            'C32 H46 F Mn N2 O2 P2'
_chemical_formula_weight         626.59
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-06-02
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2021.05.01 svn.r6f5a8f70 for OlexSys, GUI svn.r6320)
;
_cell_angle_alpha                90
_cell_angle_beta                 104.703(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.6518(2)
_cell_length_b                   15.3285(3)
_cell_length_c                   16.7761(4)
_cell_measurement_reflns_used    14180
_cell_measurement_temperature    99.97(11)
_cell_measurement_theta_max      78.9780
_cell_measurement_theta_min      3.5650
_cell_volume                     3146.91(11)
_computing_cell_refinement       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.97(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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      4.00 135.00   0.50    1.00    --   45.20  57.00   0.00  262
  2  \w      4.00 135.00   0.50    1.00    --   45.20  57.00 150.00  262
  3  \w      4.00 135.00   0.50    1.00    --   45.20  57.00  90.00  262
  4  \w      1.00 135.00   0.50    1.00    --   45.20  77.00-150.00  268
  5  \w      1.00 135.00   0.50    1.00    --   45.20  77.00  90.00  268
  6  \w    -44.00  90.00   0.50    1.00    --   45.20 -77.00-180.00  268
  7  \w     25.00 193.00   0.50   13.00    --  114.00   0.00-180.00  336
  8  \w    100.00 126.00   0.50   13.00    --  114.00 -75.00 -77.00   52
  9  \w     25.00 160.00   0.50   13.00    --  114.00 -50.00 -90.00  270
 10  \w     25.00  82.00   0.50   13.00    --  114.00 -75.00 -77.00  114
 11  \w    118.00 158.00   0.50   13.00    --  114.00  38.00  30.00   80
 12  \w     59.00 183.00   0.50   13.00    --  114.00  38.00  60.00  248
 13  \w     42.00 137.00   0.50   13.00    --  114.00 -64.00 120.00  190
 14  \w     56.00  85.00   0.50   13.00    --  114.00  38.00  30.00   58
 15  \w     25.00 161.00   0.50   13.00    --  114.00 -82.00 120.00  272
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0336847000
_diffrn_orient_matrix_UB_12      -0.0809965000
_diffrn_orient_matrix_UB_13      -0.0548468000
_diffrn_orient_matrix_UB_21      -0.1211628000
_diffrn_orient_matrix_UB_22      0.0199754000
_diffrn_orient_matrix_UB_23      -0.0061729000
_diffrn_orient_matrix_UB_31      -0.0056796000
_diffrn_orient_matrix_UB_32      0.0560164000
_diffrn_orient_matrix_UB_33      -0.0772719000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0643
_diffrn_reflns_av_unetI/netI     0.0427
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            27152
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.501
_diffrn_reflns_theta_min         3.612
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.667
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.793
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.69a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.323
_exptl_crystal_description       prism
_exptl_crystal_F_000             1328
_exptl_crystal_size_max          0.157
_exptl_crystal_size_mid          0.057
_exptl_crystal_size_min          0.036
_refine_diff_density_max         0.879
_refine_diff_density_min         -0.640
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     373
_refine_ls_number_reflns         6430
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0421
_refine_ls_R_factor_gt           0.0388
_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^)+(0.0610P)^2^+1.1535P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1030
_refine_ls_wR_factor_ref         0.1051
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5900
_reflns_number_total             6430
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c01748_si_004.cif
_cod_data_source_block           m2280
_cod_original_cell_volume        3146.90(12)
_cod_database_code               4518980
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C25H27F1N2O2P2Mn
_chemical_oxdiff_usercomment     'Quan Quan'
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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.a Ternary CH refined with riding coordinates:
 C1(H1)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C26(H26), C28(H28), C29(H29), C30(H30)
2.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,
 H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,
 H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C),
 C23(H23A,H23B,H23C)
;
_shelx_res_checksum              37719
_shelx_hkl_checksum              73336
_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 2.511
_oxdiff_exptl_absorpt_empirical_full_min 0.593