Mechanistic Studies of Hydride Transfer to Imines from a Highly Active and Chemoselective Manganate Catalyst.
Freitag, Frederik; Irrgang, Torsten; Kempe, Rhett; Journal of the American Chemical Society 141 (2019) 11677–11685; doi:10.1021/jacs.9b05024

data_4127352
_publ_section_title
;
 Mechanistic Studies of Hydride Transfer to Imines from a Highly Active
 and Chemoselective Manganate Catalyst.
;
_journal_issue                   29
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11677
_journal_page_last               11685
_journal_paper_doi               10.1021/jacs.9b05024
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety
'0.25(C93 H147 K3 Mn3 N15 O12 P6), 0.25(C4 H8 O)'
_chemical_formula_sum            'C24.25 H38.75 K0.75 Mn0.75 N3.75 O3.25 P1.5'
_chemical_formula_weight         551.82
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-02-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.90(3)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   12.840(3)
_cell_length_b                   45.110(9)
_cell_length_c                   20.490(4)
_cell_measurement_reflns_used    39500
_cell_measurement_temperature    133(2)
_cell_measurement_theta_max      28.75
_cell_measurement_theta_min      1.35
_cell_volume                     11782(4)
_computing_cell_refinement       stoe-xarea
_computing_data_collection       stoe-xarea
_computing_data_reduction        stoe-xarea
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      133.15
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.924
_diffrn_measurement_device_type  'Bruker P4'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0473
_diffrn_reflns_av_unetI/netI     0.0590
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.924
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       59
_diffrn_reflns_limit_k_min       -49
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            84619
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.924
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.662
_diffrn_reflns_theta_min         1.098
_exptl_absorpt_coefficient_mu    0.564
_exptl_absorpt_correction_T_max  0.9942
_exptl_absorpt_correction_T_min  0.9830
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.244
_exptl_crystal_description       block
_exptl_crystal_F_000             4672
_exptl_crystal_size_max          0.102
_exptl_crystal_size_mid          0.042
_exptl_crystal_size_min          0.017
_refine_diff_density_max         1.468
_refine_diff_density_min         -0.731
_refine_diff_density_rms         0.129
_refine_ls_extinction_coef       0.0030(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1305
_refine_ls_number_reflns         28052
_refine_ls_number_restraints     109
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.1474
_refine_ls_R_factor_gt           0.0983
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2702
_refine_ls_wR_factor_ref         0.3280
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15175
_reflns_number_total             28052
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b05024_si_002.cif
_cod_data_source_block           sv493_1a1_m_p2(1)n_sx
_cod_original_formula_sum
'C24.25 H38.75 K0.75 Mn0.75 N3.75 O3.25 P1.50'
_cod_database_code               4127352
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.990
_shelx_estimated_absorpt_t_min   0.945
_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. Restrained distances
 K006-O01D \\sim K006-O01E
 with sigma of 0.02
 O01D-C03Q \\sim O01E-C0AA
 with sigma of 0.02
 O01D-C23 \\sim O01E-C23A
 with sigma of 0.02
 C03Q-C3 \\sim C0AA-C3A
 with sigma of 0.02
 C3-C11 \\sim C3A-C11A
 with sigma of 0.02
 C11-C23 \\sim C11A-C23A
 with sigma of 0.02
 K006-C03Q \\sim K006-C0AA
 with sigma of 0.04
 K006-C23 \\sim K006-C23A
 with sigma of 0.04
 O01D-C3 \\sim O01E-C3A
 with sigma of 0.04
 O01D-C11 \\sim O01E-C11A
 with sigma of 0.04
 C03Q-C11 \\sim C0AA-C11A
 with sigma of 0.04
 C03Q-C23 \\sim C0AA-C23A
 with sigma of 0.04
 C3-C23 \\sim C3A-C23A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C23 \\sim C11 \\sim C3 \\sim C03Q: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002
C03L \\sim C03G \\sim C03D \\sim C03M \\sim O02U: within 2A with sigma of 0.001
and sigma for terminal atoms of 0.002
C11A \\sim C3A \\sim C23A \\sim O01E \\sim C0AA: within 2A with sigma of 0.001
and sigma for terminal atoms of 0.002
C03O \\sim C03B \\sim C03N \\sim C03J: within 2A with sigma of 0.001 and sigma
for terminal atoms of 0.002
4. Others
 Sof(C11A)=Sof(H11C)=Sof(H11D)=Sof(C3A)=Sof(H3AB)=Sof(H3AC)=Sof(C23A)=
 Sof(H23C)=Sof(H23D)=Sof(O01E)=Sof(C0AA)=Sof(H0AB)=Sof(H0AC)=1-FVAR(1)
 Sof(O01D)=Sof(C03Q)=Sof(H0CA)=Sof(H8DA)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(C11)=
 Sof(H11A)=Sof(H11B)=Sof(C23)=Sof(H23A)=Sof(H23B)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C019(H019), C01G(H01G), C01H(H01H), C01L(H01L), C01N(H01N), C01O(H01O),
 C01T(H01T), C01X(H01X), C025(H025), C028(H028), C02B(H02M), C02G(H02X)
5.b Secondary CH2 refined with riding coordinates:
 C02W(H8AA,HR), C032(H03G,H03H), C034(H03L,H03M), C035(H03N,H03O), C036(H03P,
 H03Q), C037(H03R,H03S), C038(H03T,H03U), C039(H03V,H03W), C03A(H03X,H03Y),
 C03B(H03Z,HY), C03C(H03,HZ), C03D(H2CA,H6CA), C03E(H2BA,H7CA), C03F(H3BA,H8CA),
  C03G(H3CA,H9CA), C03H(H4BA,H0DA), C03I(H5BA,H1DA), C03J(H6BA,H2DA), C03K(H7BA,
 H3DA), C03L(H4CA,H4DA), C03M(H5CA,H5DA), C03N(H8BA,H6DA), C03O(H9BA,H7DA),
 C03Q(H0CA,H8DA), C03R(H1CA,H9DA), C3(H3A,H3B), C11(H11A,H11B), C23(H23A,H23B),
 C11A(H11C,H11D), C3A(H3AB,H3AC), C23A(H23C,H23D), C0AA(H0AB,H0AC)
5.c Aromatic/amide H refined with riding coordinates:
 C01I(H01I), C01K(H01K), C01M(H01M), C01P(H01P), C01Q(H01Q), C01R(H01R),
 C01S(H01S), C01U(H01U), C01W(H01W), C01Z(H01Z), C020(H020), C024(H024),
 C02F(H02W), C02I(H02Z), C02L(H1AA)
5.d Idealised Me refined as rotating group:
 C01V(H01A,H01B,H01C), C01Y(H01D,H01E,H01F), C022(H02A,H02B,H02C), C023(H02D,
 H02E,H02F), C026(H02G,H02H,H02I), C027(H02J,H02K,H02L), C02C(H02N,H02O,H02P),
 C02D(H02Q,H02R,H02S), C02E(H02T,H02U,H02V), C02H(H02Y,H,HA), C02J(H02,HB,HC),
 C02K(H0AA,HD,HE), C02M(H2AA,HF,HG), C02O(H3AA,HH,HI), C02Q(H4AA,HJ,HK),
 C02R(H5AA,HL,HM), C02T(H6AA,HN,HO), C02V(H7AA,HP,HQ), C02X(H9AA,HS,HT),
 C02Y(H0BA,HU,HV), C02Z(H1BA,HW,HX), C030(H03A,H03B,H03C), C031(H03D,H03E,H03F),
  C033(H03I,H03J,H03K)
;
_shelx_res_checksum              700
_shelx_hkl_checksum              79589
_shelx_fab_checksum              55767
_olex2_submission_special_instructions 'No special instructions were received'