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_4518981
_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 H47 Mn N2 O2 P2, 0.5[C6H6]'
_chemical_formula_sum            'C32 H47 Mn N2 O2 P2'
_chemical_formula_weight         608.59
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-11-10
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.9596(13)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.92524(18)
_cell_length_b                   16.7518(2)
_cell_length_c                   16.3352(2)
_cell_measurement_reflns_used    19204
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      78.4880
_cell_measurement_theta_min      3.8080
_cell_volume                     3460.14(8)
_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 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.995
_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    -44.00  90.00   0.50    1.00    --   45.10 -57.00-150.00  268
  2  \w      4.00 134.00   0.50    1.00    --   45.10  57.00-150.00  260
  3  \w      4.00 134.00   0.50    1.00    --   45.10  57.00-180.00  260
  4  \w    -44.00  90.00   0.50    1.00    --   45.10 -77.00 -60.00  268
  5  \w      4.00 131.00   0.50    1.00    --   45.10  57.00  90.00  254
  6  \w     76.00 134.00   0.50    1.00    --   45.10  57.00 -30.00  116
  7  \w      2.00  29.00   0.50    1.00    --   45.10  38.00   0.00   54
  8  \w     70.00 186.00   0.50    5.00    --  114.00  50.00-180.00  232
  9  \w     30.00  64.00   0.50    5.00    --  114.00 -82.00   0.00   68
 10  \w    127.00 170.00   0.50    5.00    --  114.00  77.00  90.00   86
 11  \w     72.00  98.00   0.50    5.00    --  114.00 -82.00   0.00   52
 12  \w     81.00 160.00   0.50    5.00    --  114.00 -82.00-150.00  158
 13  \w     29.00  67.00   0.50    5.00    --  114.00 -38.00-180.00   76
 14  \w     69.00 203.00   0.50    5.00    --  114.00  41.00  99.69  268
 15  \w     25.00 159.00   0.50    5.00    --  114.00 -82.00 -90.00  268
 16  \w     75.00 129.00   0.50    5.00    --  114.00 -82.00 -60.00  108
 17  \w     41.00  66.00   0.50    5.00    --  114.00 -82.00 -60.00   50
 18  \w     85.00 111.00   0.50    5.00    --  114.00 -38.00-180.00   52
 19  \w     74.00 102.00   0.50    5.00    --  114.00 -82.00 150.00   56
 20  \w     75.00 111.00   0.50    5.00    --  114.00  77.00  90.00   72
 21  \w    119.00 203.00   0.50    5.00    --  114.00  82.00   0.00  168
;
_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      -0.0275495000
_diffrn_orient_matrix_UB_12      0.0657660000
_diffrn_orient_matrix_UB_13      -0.0669743000
_diffrn_orient_matrix_UB_21      -0.0146257000
_diffrn_orient_matrix_UB_22      -0.0638753000
_diffrn_orient_matrix_UB_23      -0.0692904000
_diffrn_orient_matrix_UB_31      -0.1177123000
_diffrn_orient_matrix_UB_32      -0.0073826000
_diffrn_orient_matrix_UB_33      0.0036127000
_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  0.0367
_diffrn_reflns_av_unetI/netI     0.0273
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            29932
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.504
_diffrn_reflns_theta_min         3.823
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.187
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.355
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.168
_exptl_crystal_description       plate
_exptl_crystal_F_000             1296
_exptl_crystal_size_max          0.283
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.451
_refine_diff_density_min         -0.430
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     426
_refine_ls_number_reflns         7042
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0350
_refine_ls_R_factor_gt           0.0332
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0427P)^2^+1.7918P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0860
_refine_ls_wR_factor_ref         0.0870
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6651
_reflns_number_total             7042
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c01748_si_002.cif
_cod_data_source_block           m2270
_cod_original_cell_volume        3460.15(8)
_cod_database_code               4518981
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C32H47N2O2P2Mn1
_chemical_oxdiff_usercomment     'Quan Quan  - side of the vial'
_reflns_odcompleteness_completeness 99.63
_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. Others
 Sof(P7)=Sof(C1A)=Sof(H1A)=Sof(C8A)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=
 Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C11A)=Sof(H11D)=Sof(H11E)=
 Sof(H11F)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C15A)=Sof(H15D)=
 Sof(H15E)=Sof(H15F)=Sof(C25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(H27A)=
 Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30A)=1-FVAR(1)
 Sof(P1)=Sof(C1)=Sof(H1)=Sof(C8)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=
 Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C13)=
 Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C25)=
 Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28)=Sof(C29)=Sof(H29)=
 Sof(C30)=Sof(H30)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C1(H1), C1A(H1A)
3.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B)
3.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30),
 C26A(H26A), C27A(H27A), C28A(H28A), C29A(H29A), C30A(H30A)
3.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C14(H14A,H14B,H14C), C9(H9A,
 H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C),
 C15(H15A,H15B,H15C), C9A(H9AA,H9AB,H9AC), C10A(H10D,H10E,H10F), C11A(H11D,H11E,
 H11F), C13A(H13D,H13E,H13F), C15A(H15D,H15E,H15F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              21938
_shelx_hkl_checksum              96452
_shelx_fab_checksum              96348
_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 2.030
_oxdiff_exptl_absorpt_empirical_full_min 0.684