Lewis Acid Enhancement of Proton Induced CO<sub>2</sub> Cleavage: Bond Weakening and Ligand Residence Time Effects.
Buss, Joshua A.; VanderVelde, David G.; Agapie, Theodor; Journal of the American Chemical Society 140 (2018) 10121–10125; doi:10.1021/jacs.8b05874

data_4132731
_publ_section_title
;
 Lewis Acid Enhancement of Proton Induced CO<sub>2</sub> Cleavage: Bond
 Weakening and Ligand Residence Time Effects.
;
_journal_issue                   32
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10121
_journal_page_last               10125
_journal_paper_doi               10.1021/jacs.8b05874
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C48 H40 B F15 Mo N2 P2'
_chemical_formula_sum            'C48 H40 B F15 Mo N2 P2'
_chemical_formula_weight         1098.51
_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
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-02-16
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155),
SHELXL-2014,
and manual edit
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.5019(11)
_cell_length_b                   9.3504(5)
_cell_length_c                   20.5286(9)
_cell_measurement_reflns_used    6871
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.17
_cell_measurement_theta_min      2.55
_cell_volume                     4511.2(4)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2014.11-0 (Bruker-AXS, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'DIAMOND 3 (Crystal Impact, 1999)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'XT-2014/4 (Sheldrick, 2012)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD Area Detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'Bruker APEXII CCD'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker KAPPA APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0577
_diffrn_reflns_av_unetI/netI     0.0604
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            38913
_diffrn_reflns_point_group_measured_fraction_full 0.893
_diffrn_reflns_point_group_measured_fraction_max 0.826
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         31.511
_diffrn_reflns_theta_min         1.984
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_current           30
_diffrn_source_power             1.5
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.462
_exptl_absorpt_correction_T_max  0.7468
_exptl_absorpt_correction_T_min  0.6815
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0587 before and 0.0531 after correction. The Ratio of minimum to maximum transmission is 0.9126. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.617
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             2216
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.493
_refine_diff_density_min         -0.580
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Flack x determined using 3403 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.020(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.008
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     996
_refine_ls_number_reflns         12409
_refine_ls_number_restraints     1321
_refine_ls_restrained_S_all      0.982
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0371
_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^)+(0.0284P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0668
_refine_ls_wR_factor_ref         0.0726
_reflns_Friedel_coverage         0.611
_reflns_Friedel_fraction_full    0.779
_reflns_Friedel_fraction_max     0.642
_reflns_number_gt                9994
_reflns_number_total             12409
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b05874_si_001.cif
_cod_data_source_block           3
_cod_database_code               4132731
_shelxl_version_number           2014-7
_shelx_estimated_absorpt_t_max   0.951
_shelx_estimated_absorpt_t_min   0.913
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 B1A, B1B, C31A, C32A, C33A, C34A, C35A, C36A, F1A, F2A, F3A, F4A, F5A, C37A,
 C38A, C39A, C40A, C41A, C42A, F6A, F7A, F8A, F9A, F10A, C43A, C44A, C45A, C46A,
  C47A, C48A, F11A, F12A, F13A, F14A, F15A, B1B, C31B, C32B, C33B, C34B, C35B,
 C36B, F1B, F2B, F3B, F4B, F5B, C37B, C38B, C39B, C40B, C41B, C42B, F6B, F7B,
 F8B, F9B, F10B, C43B, C44B, C45B, C46B, C47B, C48B, F11B, F12B, F13B, F14B,
 F15B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
B1A \\sim B1B \\sim C31A \\sim C32A \\sim C33A \\sim C34A \\sim C35A \\sim C36A
\\sim F1A \\sim F2A \\sim F3A \\sim F4A \\sim F5A \\sim C37A \\sim C38A \\sim
C39A \\sim C40A \\sim C41A \\sim C42A \\sim F6A \\sim F7A \\sim F8A \\sim F9A
\\sim F10A \\sim C43A \\sim C44A \\sim C45A \\sim C46A \\sim C47A \\sim C48A
\\sim F11A \\sim F12A \\sim F13A \\sim F14A \\sim F15A \\sim B1B \\sim C31B
\\sim C32B \\sim C33B \\sim C34B \\sim C35B \\sim C36B \\sim F1B \\sim F2B
\\sim F3B \\sim F4B \\sim F5B \\sim C37B \\sim C38B \\sim C39B \\sim C40B \\sim
C41B \\sim C42B \\sim F6B \\sim F7B \\sim F8B \\sim F9B \\sim F10B \\sim C43B
\\sim C44B \\sim C45B \\sim C46B \\sim C47B \\sim C48B \\sim F11B \\sim F12B
\\sim F13B \\sim F14B \\sim F15B: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.01
4. Others
 Sof(C25A)=Sof(H25A)=Sof(C26A)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C27A)=
 Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(H29A)=
 Sof(H29B)=Sof(H29C)=Sof(C30A)=Sof(H30A)=Sof(H30B)=Sof(H30C)=1-FVAR(1)
 Sof(C25B)=Sof(H25B)=Sof(C26B)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C27B)=
 Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(C28B)=Sof(H28B)=Sof(C29B)=Sof(H29D)=
 Sof(H29E)=Sof(H29F)=Sof(C30B)=Sof(H30D)=Sof(H30E)=Sof(H30F)=FVAR(1)
 Sof(B1B)=Sof(C31B)=Sof(C32B)=Sof(C33B)=Sof(C34B)=Sof(C35B)=Sof(C36B)=Sof(F1B)=
 Sof(F2B)=Sof(F3B)=Sof(F4B)=Sof(F5B)=Sof(C37B)=Sof(C38B)=Sof(C39B)=Sof(C40B)=
 Sof(C41B)=Sof(C42B)=Sof(F6B)=Sof(F7B)=Sof(F8B)=Sof(F9B)=Sof(F10B)=Sof(C43B)=
 Sof(C44B)=Sof(C45B)=Sof(C46B)=Sof(C47B)=Sof(C48B)=Sof(F11B)=Sof(F12B)=
 Sof(F13B)=Sof(F14B)=Sof(F15B)=1-FVAR(2)
 Sof(B1A)=Sof(C31A)=Sof(C32A)=Sof(C33A)=Sof(C34A)=Sof(C35A)=Sof(C36A)=Sof(F1A)=
 Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(C37A)=Sof(C38A)=Sof(C39A)=Sof(C40A)=
 Sof(C41A)=Sof(C42A)=Sof(F6A)=Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(F10A)=Sof(C43A)=
 Sof(C44A)=Sof(C45A)=Sof(C46A)=Sof(C47A)=Sof(C48A)=Sof(F11A)=Sof(F12A)=
 Sof(F13A)=Sof(F14A)=Sof(F15A)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C19(H19), C22(H22), C25A(H25A), C25B(H25B), C28A(H28A), C28B(H28B)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C15(H15), C16(H16), C17(H17), C18(H18)
5.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C26A(H26A,H26B,H26C), C26B(H26D,H26E,H26F), C27A(H27A,H27B,H27C),
 C27B(H27D,H27E,H27F), C29A(H29A,H29B,H29C), C29B(H29D,H29E,H29F), C30A(H30A,
 H30B,H30C), C30B(H30D,H30E,H30F)
;
_shelx_res_checksum              52401
_shelx_hkl_checksum              66671
_olex2_submission_special_instructions 'No special instructions were received'