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_4518982
_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_absolute_configuration ad
_chemical_formula_moiety         'C34 H51 Mn N2 O2 P2, C F3 O3 S, C H2 Cl2'
_chemical_formula_sum            'C36 H53 Cl2 F3 Mn N2 O5 P2 S'
_chemical_formula_weight         870.64
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-11-08
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.11.05 svn.r0a1fe1be for OlexSys, GUI svn.r6182)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1759(3)
_cell_length_b                   13.3287(3)
_cell_length_c                   25.6006(6)
_cell_measurement_reflns_used    24108
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      31.8490
_cell_measurement_theta_min      1.5850
_cell_volume                     4154.69(17)
_computing_cell_refinement       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 300K'
_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     26.00  51.00   0.50    5.00    --  -19.06  19.00 -60.00   50
  2  \w     -4.00  40.00   0.50    5.00    --  -19.06  84.00 -73.00   88
  3  \w      4.00  59.00   0.50    5.00    --  -19.06  77.00  60.00  110
  4  \w    -26.00  21.00   0.50    5.00    --  -19.06  19.00 -60.00   94
  5  \w    -58.00 -28.00   0.50    5.00    --  -19.06  77.00  60.00   60
  6  \w    -63.00 -36.00   0.50    5.00    --  -19.06  84.00 -73.00   54
  7  \w     19.00  70.00   0.50    5.00    --   17.81 -99.00 -90.00  102
  8  \w      0.00  68.00   0.50    5.00    --   17.81 -99.00  30.00  136
  9  \w     49.00  75.00   0.50    5.00    --   17.81-113.00  84.00   52
 10  \w    -39.00 -13.00   0.50    5.00    --  -19.52 113.00 176.00   52
 11  \w    -12.00  14.00   0.50    5.00    --  -19.52  19.00  30.00   52
 12  \w     30.00  64.00   0.50    5.00    --  -19.52  19.00  30.00   68
 13  \w    -83.00 -43.00   0.50    5.00    --  -19.52-178.00  30.00   80
 14  \w    -68.00 -43.00   0.50    5.00    --  -19.52 -41.00 -54.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 300K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0276258000
_diffrn_orient_matrix_UB_12      -0.0339325000
_diffrn_orient_matrix_UB_13      0.0168089000
_diffrn_orient_matrix_UB_21      0.0110925000
_diffrn_orient_matrix_UB_22      0.0397860000
_diffrn_orient_matrix_UB_23      0.0176345000
_diffrn_orient_matrix_UB_31      -0.0500599000
_diffrn_orient_matrix_UB_32      -0.0098830000
_diffrn_orient_matrix_UB_33      0.0132067000
_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  0.0707
_diffrn_reflns_av_unetI/netI     0.0518
_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       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            51677
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.281
_diffrn_reflns_theta_min         1.591
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.629
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.497
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.80a (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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.392
_exptl_crystal_description       prism
_exptl_crystal_F_000             1820
_exptl_crystal_size_max          0.182
_exptl_crystal_size_mid          0.174
_exptl_crystal_size_min          0.053
_refine_diff_density_max         1.133
_refine_diff_density_min         -0.756
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 3630 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.001(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     491
_refine_ls_number_reflns         10302
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0536
_refine_ls_R_factor_gt           0.0465
_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^)+(0.0544P)^2^+2.3272P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1097
_refine_ls_wR_factor_ref         0.1135
_reflns_Friedel_coverage         0.806
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                9201
_reflns_number_total             10302
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c01748_si_003.cif
_cod_data_source_block           m2269
_cod_database_code               4518982
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C35H50N2O5S1F3O5P2Mn1
_chemical_oxdiff_usercomment     'Quan Quan'
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(H36D)=Sof(H36C)=Sof(Cl1A)=Sof(Cl2A)=1-FVAR(1)
 Sof(H36A)=Sof(H36B)=Sof(Cl1)=Sof(Cl2)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C1(H1), C25(H25)
3.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C36(H36A,H36B), C36(H36D,H36C)
3.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31)
3.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), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              88324
_shelx_hkl_checksum              43606
_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 1.240
_oxdiff_exptl_absorpt_empirical_full_min 0.822