Silver(II) and Silver(III) Intermediates in Alkene Aziridination with a Dinuclear Silver(I) Nitrene Transfer Catalyst
Elkoush, Tasneem; Mak, Choi L.; Paley, Daniel W.; Campbell, Michael G.; ACS Catalysis  (2020) 4820–; doi:10.1021/acscatal.0c00065

data_4517554
_publ_section_title
;
 Silver(II) and Silver(III) Intermediates in Alkene Aziridination with a
 Dinuclear Silver(I) Nitrene Transfer Catalyst
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              4820
_journal_paper_doi               10.1021/acscatal.0c00065
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C39 H45 Ag N4 O4 S2, N O3, C H2 Cl2, O'
_chemical_formula_sum            'C40 H47 Ag Cl2 N5 O8 S2'
_chemical_formula_weight         968.71
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-02-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.4684(4)
_cell_length_b                   13.4202(2)
_cell_length_c                   15.4089(2)
_cell_measurement_reflns_used    18692
_cell_measurement_temperature    99.96(14)
_cell_measurement_theta_max      72.7180
_cell_measurement_theta_min      3.9270
_cell_volume                     4232.67(12)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.96(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0549
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.973
_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   -104.00 -17.00   1.00    2.00    --  -37.78 -77.00   0.00   87
  2  \w   -106.00 -19.00   1.00    2.00    --  -37.78 -37.00-120.00   87
  3  \w    -99.00 -55.00   1.00    2.00    --  -37.78 138.00 110.00   44
  4  \w   -110.00 -43.00   1.00    2.00    --  -37.78-178.00   0.00   67
  5  \w    -87.00 -36.00   1.00    2.00    --  -37.78-178.00  30.00   51
  6  \w    -56.00  31.00   1.00    2.00    --  -37.78  37.00-120.00   87
  7  \w    -98.00 -43.00   1.00    2.00    --  -37.78-178.00 -60.00   55
  8  \w     58.00  92.00   1.00    2.00    --   37.78-138.00  48.00   34
  9  \w     80.00 106.00   1.00    2.00    --   37.78 178.00   0.00   26
 10  \w     41.00  70.00   1.00   10.00    --  111.00 -30.00-180.00   29
 11  \w     91.00 153.00   1.00   10.00    --  111.00  30.00  60.00   62
 12  \w     43.00  90.00   1.00   10.00    --  111.00 -30.00-150.00   47
 13  \w    102.00 174.00   1.00   10.00    --  111.00 111.00-120.00   72
 14  \w     42.00 113.00   1.00   10.00    --  111.00-111.00  60.00   71
 15  \w     93.00 120.00   1.00   10.00    --  111.00 -61.00 -90.00   27
 16  \w     93.00 124.00   1.00   10.00    --  111.00 -69.00 164.21   31
 17  \w     44.00  78.00   1.00   10.00    --  111.00 -45.00 -60.00   34
 18  \w     58.00  98.00   1.00   10.00    --  111.00 178.00  90.00   40
 19  \w     64.00 126.00   1.00   10.00    --  111.00 -45.00 120.00   62
 20  \w    121.00 177.00   1.00   10.00    --  111.00  45.00-150.00   56
 21  \w     43.00 120.00   1.00   10.00    --  111.00-131.00-135.00   77
 22  \w     59.00  89.00   1.00   10.00    --  111.00 -61.00 -90.00   30
 23  \w    100.00 130.00   1.00   10.00    --  111.00 -30.00-150.00   30
 24  \w    112.00 144.00   1.00   10.00    --  111.00  30.00  30.00   32
 25  \w     59.00  86.00   1.00   10.00    --  111.00 -94.00  60.00   27
 26  \w     58.00  90.00   1.00   10.00    --  111.00 -94.00-120.00   32
 27  \w     69.00  96.00   1.00   10.00    --  111.00-111.00 -30.00   27
 28  \w     57.00  84.00   1.00   10.00    --  111.00 -45.00  30.00   27
 29  \w     72.00  78.00   1.00   10.00    --  111.00 -94.00-180.00    6
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0133762000
_diffrn_orient_matrix_UB_12      0.1067688000
_diffrn_orient_matrix_UB_13      0.0321484000
_diffrn_orient_matrix_UB_21      -0.0740465000
_diffrn_orient_matrix_UB_22      -0.0184387000
_diffrn_orient_matrix_UB_23      -0.0083533000
_diffrn_orient_matrix_UB_31      -0.0017710000
_diffrn_orient_matrix_UB_32      -0.0380055000
_diffrn_orient_matrix_UB_33      0.0943280000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0734
_diffrn_reflns_av_unetI/netI     0.0647
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            26231
_diffrn_reflns_point_group_measured_fraction_full 0.785
_diffrn_reflns_point_group_measured_fraction_max 0.771
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.923
_diffrn_reflns_theta_min         3.293
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.383
_exptl_absorpt_correction_T_max  0.960
_exptl_absorpt_correction_T_min  0.159
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.520
_exptl_crystal_description       plate
_exptl_crystal_F_000             1996
_exptl_crystal_size_max          0.284
_exptl_crystal_size_mid          0.093
_exptl_crystal_size_min          0.016
_refine_diff_density_max         0.938
_refine_diff_density_min         -0.738
_refine_diff_density_rms         0.121
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   -0.005(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     601
_refine_ls_number_reflns         6521
_refine_ls_number_restraints     85
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0577
_refine_ls_R_factor_gt           0.0541
_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^)+(0.0988P)^2^+0.5616P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1339
_refine_ls_wR_factor_ref         0.1380
_reflns_Friedel_coverage         0.524
_reflns_Friedel_fraction_full    0.575
_reflns_Friedel_fraction_max     0.553
_reflns_number_gt                6093
_reflns_number_total             6521
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c00065_si_003.cif
_cod_data_source_block           cmpd3_revised
_cod_database_code               4517554
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         Ag2C20H20N6
_reflns_odcompleteness_completeness 96.11
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     73.59
_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. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1A with sigma of 0.01 and sigma
for terminal atoms of 0.02
3. Rigid body (RIGU) restrains
 C17, C18, C19, C20, C18B, C19B, C20B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C61, Cl62, Cl63, C71, Cl72, Cl73
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Same fragment restrains
{C14, C15, C16, C17, C18B, C19B, C20B} sigma for 1-2: 0.02, 1-3: 0.04
as
{C14, C15, C16, C17, C18, C19, C20}
{C71, Cl72, Cl73} sigma for 1-2: 0.02, 1-3: 0.04
{C61, Cl63, Cl62} sigma for 1-2: 0.02, 1-3: 0.04
{C71, Cl73, Cl72} sigma for 1-2: 0.02, 1-3: 0.04
as
{C61, Cl62, Cl63}
5. Others
 Sof(C18B)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C19B)=Sof(H19D)=Sof(H19E)=
 Sof(H19F)=Sof(C20B)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(1)
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(1)
 Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(Cl72)=Sof(Cl73)=1-FVAR(2)
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(Cl62)=Sof(Cl63)=FVAR(2)
 Sof(O1)=1-FVAR(3)
 Sof(O1)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C61(H61A,H61B), C71(H71A,H71B)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C13(H13), C15(H15), C23(H23), C25(H25), C26(H26),
 C36(H36), C37(H37), C38(H38), C39(H39), C40(H40), C46(H46), C47(H47), C48(H48),
  C49(H49), C50(H50)
6.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C18B(H18D,H18E,H18F), C19B(H19D,H19E,
 H19F), C20B(H20D,H20E,H20F), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C),
 C30(H30A,H30B,H30C)
;
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.761
_oxdiff_exptl_absorpt_empirical_full_min 0.661