Mn(i) phosphine-amino-phosphinites: a highly modular class of pincer complexes for enantioselective transfer hydrogenation of aryl-alkyl ketones
Jayaprakash, Harikrishnan; Dalton Transactions  (2021) –; doi:10.1039/D1DT02257A

data_7708509
_publ_section_title
;
 Mn(i) phosphine-amino-phosphinites: a highly modular class of pincer
 complexes for enantioselective transfer hydrogenation of aryl-alkyl
 ketones
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT02257A
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C39 H37 Br Mn N O3 P2'
_chemical_formula_sum            'C39 H37 Br Mn N O3 P2'
_chemical_formula_weight         764.48
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-05-17
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-05-17 deposited with the CCDC.	2021-10-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.7480(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.5751(3)
_cell_length_b                   29.5477(10)
_cell_length_c                   12.0766(4)
_cell_measurement_reflns_used    9917
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      80.481
_cell_measurement_theta_min      2.991
_cell_volume                     3573.4(2)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_collection       'Bruker APEX3'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker Photon II area detector'
_diffrn_detector_area_resol_mean 7.39
_diffrn_detector_type            'CPAD area detector'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.970
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'double mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0456
_diffrn_reflns_av_unetI/netI     0.0446
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            53870
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.947
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         81.164
_diffrn_reflns_theta_min         2.991
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.460
_exptl_absorpt_correction_T_max  0.7543
_exptl_absorpt_correction_T_min  0.5477
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1351 before and 0.0706 after correction.
The Ratio of minimum to maximum transmission is 0.7261.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.421
_exptl_crystal_description       plate
_exptl_crystal_F_000             1568
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.496
_refine_diff_density_min         -0.441
_refine_diff_density_rms         0.085
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.014(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     873
_refine_ls_number_reflns         14930
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0537
_refine_ls_R_factor_gt           0.0531
_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^)+(0.0392P)^2^+16.1659P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1296
_refine_ls_wR_factor_ref         0.1308
_reflns_Friedel_coverage         0.914
_reflns_Friedel_fraction_full    0.971
_reflns_Friedel_fraction_max     0.923
_reflns_number_gt                14769
_reflns_number_total             14930
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt02257a2.cif
_cod_data_source_block           3a
_cod_database_code               7708509
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.611
_shelx_estimated_absorpt_t_min   0.291
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2. Restrained distances
 Mn2-C78A \\sim Mn2-C77
 with sigma of 0.01
 Mn1-C38 \\sim Mn1-C38A
 with sigma of 0.01
 O1-C38 \\sim O1A-C38A
 with sigma of 0.01
 O4-C77 \\sim O5A-C78A
 with sigma of 0.01
 Mn1-O1 \\sim Mn1-O1A
 with sigma of 0.02
3. Others
 Sof(Br2A)=Sof(O5A)=Sof(C78A)=1-FVAR(1)
 Sof(Br2)=Sof(O5)=Sof(C78)=FVAR(1)
 Sof(Br1A)=Sof(O1A)=Sof(C38A)=1-FVAR(2)
 Sof(Br1)=Sof(O1)=Sof(C38)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 N1(H1), C20(H20), C21(H21), N2(H2A), C59(H59), C60(H60)
4.b Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,
 H25B), C58(H58A,H58B), C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B),
 C64(H64A,H64B)
4.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C27(H27), C28(H28), C29(H29),
  C30(H30), C31(H31), C33(H33), C34(H34), C35(H35), C36(H36), C37(H37),
 C41(H41), C42(H42), C43(H43), C44(H44), C45(H45), C47(H47), C48(H48), C49(H49),
  C50(H50), C51(H51), C53(H53), C54(H54), C55(H55), C56(H56), C66(H66),
 C67(H67), C68(H68), C69(H69), C70(H70), C72(H72), C73(H73), C74(H74), C75(H75),
  C76(H76)
;
_shelx_res_checksum              77207
_shelx_hkl_checksum              26686
_olex2_exptl_crystal_mounting_method tip-mounted
_olex2_submission_special_instructions 'No special instructions were received'