Manganese 2-phosphinophosphinine precatalysts for methanol/ethanol upgrading to isobutanol.
Ward, Daniel J.; Marseglia, Margot; Saccomando, Daniel J.; Walker, Gary; Mansell, Stephen M.; Dalton transactions (Cambridge, England : 2003) 53 (2024) 16598–16609; doi:10.1039/d4dt02142h

data_7717098
_publ_section_title
;
 Manganese 2-phosphinophosphinine precatalysts for methanol/ethanol
 upgrading to isobutanol.
;
_journal_issue                   40
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              16598
_journal_page_last               16609
_journal_paper_doi               10.1039/d4dt02142h
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         '2(C24 H24 Br Mn O3 P2 Si), C7 H8, C3 H7'
_chemical_formula_sum            'C58 H63 Br2 Mn2 O6 P4 Si2'
_chemical_formula_weight         1305.84
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-08-20 deposited with the CCDC.	2024-09-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 111.7600(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   46.5632(9)
_cell_length_b                   14.5689(3)
_cell_length_c                   19.2839(3)
_cell_measurement_reflns_used    9947
_cell_measurement_temperature    111(2)
_cell_measurement_theta_max      69.86
_cell_measurement_theta_min      3.20
_cell_volume                     12149.6(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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 (Sheldrick, 2015)'
_diffrn_ambient_temperature      111.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0861
_diffrn_reflns_av_unetI/netI     0.0402
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       50
_diffrn_reflns_limit_h_min       -56
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            104426
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.065
_diffrn_reflns_theta_min         3.201
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    6.673
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.5581
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1369 before and 0.0803 after correction. The Ratio of minimum to maximum transmission is 0.7409. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.428
_exptl_crystal_description       plate
_exptl_crystal_F_000             5336
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.954
_refine_diff_density_min         -0.754
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     687
_refine_ls_number_reflns         11534
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0815
_refine_ls_R_factor_gt           0.0604
_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^)+(0.0655P)^2^+84.8903P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1407
_refine_ls_wR_factor_ref         0.1544
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8998
_reflns_number_total             11534
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt02142h2.cif
_cod_data_source_block           2
_cod_depositor_comments
'Adding full bibliography for 7717098--7717101.cif.'
_cod_database_code               7717098
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.776
_shelx_estimated_absorpt_t_min   0.380
_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. Rigid bond restraints
 Br2A, Br2B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
Br2A \\sim Br2B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
4. Rigid body (RIGU) restrains
 Br2B, Mn2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Br2B)=1-FVAR(1)
 Sof(Br2A)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C56(H56A,H56B), C57(H57A,H57B)
6.b Aromatic/amide H refined with riding coordinates:
 C27(H27), C28(H28), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36),
 C38(H38), C39(H39), C40(H40), C41(H41), C42(H42), C3(H3), C4(H4), C8(H8),
 C9(H9), C10(H10), C11(H11), C12(H12), C14(H14), C15(H15), C16(H16), C17(H17),
 C18(H18), C50(H50), C51(H51), C52(H52), C53(H53), C54(H54)
6.c Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,
 H45C), C6(H6A,H6B,H6C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,
 H21B,H21C), C55(H55A,H55B,H55C), C58(H58A,H58B,H58C)
;
_shelx_res_checksum              51181
_shelx_hkl_checksum              59569
_olex2_submission_special_instructions 'No special instructions were received'