Manganese Pincer Complexes for the Base-Free, Acceptorless Dehydrogenative Coupling of Alcohols to Esters: Development, Scope, and Understanding
Nguyen, Duc Hanh; Trivelli, Xavier; Capet, Frédéric; Paul, Jean-François; Dumeignil, Franck; Gauvin, Régis M.; ACS Catalysis 7 (2017) 2022–; doi:10.1021/acscatal.6b03554

data_4514057
_publ_section_title
;
 Manganese Pincer Complexes for the Base-Free, Acceptorless
 Dehydrogenative Coupling of Alcohols to Esters: Development, Scope, and
 Understanding
;
_journal_issue                   3
_journal_name_full               'ACS Catalysis'
_journal_page_first              2022
_journal_paper_doi               10.1021/acscatal.6b03554
_journal_volume                  7
_journal_year                    2017
_chemical_formula_moiety         'C25 H44 Mn N O3 P2'
_chemical_formula_sum            'C25 H44 Mn N O3 P2'
_chemical_formula_weight         523.49
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_space_group_name_Hall  'P 2c -2n'
_symmetry_space_group_name_H-M   'P n a 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-09-19
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   30.3732(14)
_cell_length_b                   11.6836(6)
_cell_length_c                   7.6516(4)
_cell_measurement_reflns_used    8853
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      25.36
_cell_measurement_theta_min      2.66
_cell_volume                     2715.3(2)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015b)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0526
_diffrn_reflns_av_unetI/netI     0.0445
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            35949
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        25.439
_diffrn_reflns_theta_max         25.439
_diffrn_reflns_theta_min         1.341
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.629
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6940
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0766 before and 0.0582 after correction.
The Ratio of minimum to maximum transmission is 0.9313.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.281
_exptl_crystal_description       block
_exptl_crystal_F_000             1120
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.217
_refine_diff_density_min         -0.245
_refine_diff_density_rms         0.048
_refine_ls_abs_structure_details
;
 Flack x determined using 1755 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.009(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     301
_refine_ls_number_reflns         4914
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0386
_refine_ls_R_factor_gt           0.0299
_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^)+(0.0255P)^2^+0.5162P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0575
_refine_ls_wR_factor_ref         0.0602
_reflns_Friedel_coverage         0.815
_reflns_Friedel_fraction_full    0.957
_reflns_Friedel_fraction_max     0.957
_reflns_number_gt                4401
_reflns_number_total             4914
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs6b03554_si_002.cif
_cod_data_source_block           pna21
_cod_database_code               4514057
_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.a Ternary CH refined with riding coordinates:
 C1(H1A), C14(H14), C11(H11), C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C8(H8A,H8B), C10(H10A,H10B), C7(H7A,H7B), C17(H17A,H17B)
2.c Aromatic/amide H refined with riding coordinates:
 C19(H19), C23(H23), C22(H22), C20(H20), C21(H21)
2.d Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C5(H5A,H5B,H5C),
 C15(H15A,H15B,H15C), C6(H6A,H6B,H6C), C16(H16A,H16B,H16C), C3(H3A,H3B,H3C)
;
_shelx_res_checksum              79399
_shelx_hkl_checksum              25567
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'