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_4132733
_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         '1(C31 H40 Mo O P2), C32 H12 B F24, 2(C6 H6)'
_chemical_formula_sum            'C75 H64 B F24 Mo O P2'
_chemical_formula_weight         1605.95
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-05-31
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
SHELXL-2014,
and manual edit
;
_cell_angle_alpha                111.964(2)
_cell_angle_beta                 100.228(3)
_cell_angle_gamma                92.383(3)
_cell_formula_units_Z            2
_cell_length_a                   13.0216(7)
_cell_length_b                   16.2787(8)
_cell_length_c                   18.3832(9)
_cell_measurement_reflns_used    9394
_cell_measurement_temperature    100
_cell_measurement_theta_max      33.16
_cell_measurement_theta_min      2.22
_cell_volume                     3531.5(3)
_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 0.996
_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  0.0350
_diffrn_reflns_av_unetI/netI     0.0147
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            357364
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         33.250
_diffrn_reflns_theta_min         1.358
_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    0.340
_exptl_absorpt_correction_T_max  0.7465
_exptl_absorpt_correction_T_min  0.7098
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0493 before and 0.0470 after correction. The Ratio of minimum to maximum transmission is 0.9508. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.510
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1630
_exptl_crystal_size_max          0.341
_exptl_crystal_size_mid          0.266
_exptl_crystal_size_min          0.166
_refine_diff_density_max         0.930
_refine_diff_density_min         -0.975
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.242
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1178
_refine_ls_number_reflns         27056
_refine_ls_number_restraints     305
_refine_ls_restrained_S_all      1.249
_refine_ls_R_factor_all          0.0473
_refine_ls_R_factor_gt           0.0430
_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^)+(0.0160P)^2^+4.1176P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0977
_refine_ls_wR_factor_ref         0.0996
_reflns_Friedel_coverage         0.000
_reflns_number_gt                24961
_reflns_number_total             27056
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b05874_si_001.cif
_cod_data_source_block           6
_cod_depositor_comments
;
The following automatic conversions were performed:

data name '__diffrn_measurement_device_type' was replaced with
'_diffrn_measurement_device_type'.

Automatic conversion script
Id: cif_correct_tags 6909 2019-04-08 15:41:33Z antanas 
;
_cod_database_code               4132733
_shelxl_version_number           2014-7
_shelx_estimated_absorpt_t_max   0.946
_shelx_estimated_absorpt_t_min   0.893
_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 body (RIGU) restrains
 F16A, F16B, F17A, F18B, F18A, F17B, C55, C54
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Mo1B, P1B, P2B, O1B, C1B, C2B, C3B, C4B, C5B, C6B, C7B, C8B, C9B, C10B, C11B,
 C12B, C13B, C14B, C15B, C16B, C17B, C18B, C19B, C20B, C21B, C22B, C23B, C24B,
 C25B, C26B, C27B, C28B, C29B, C30B, C31B, H6B, H5B, H3B, H2B, H9B, H10B, H11B,
 H12B, H15B, H16B, H17B, H18B, H19B, H20D, H20E, H20F, H21D, H21E, H21F, H22B,
 H23D, H23E, H23F, H24D, H24E, H24F, H25B, H26D, H26E, H26F, H27D, H27E, H27F,
 H28B, H29D, H29E, H29F, H30D, H30E, H30F
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C62, C63, F22A, F23A, F24A, F22B, F23B, F24B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C60, C61, F19A, F20A, F21A, F19B, F20B, F21B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Same fragment restrains
{Mo1A, P1A, P2A, O1A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A, C10A, C11A,
C12A, C13A, C14A, C15A, C16A, C17A, C18A, C19A, C20A, C21A, C22A, C23A, C24A,
C25A, C26A, C27A, C28A, C29A, C30A, C31A} sigma for 1-2: 0.02, 1-3: 0.04
as
{Mo1B, P1B, P2B, O1B, C1B, C2B, C3B, C4B, C5B, C6B, C7B, C8B, C9B, C10B, C11B,
C12B, C13B, C14B, C15B, C16B, C17B, C18B, C19B, C20B, C21B, C22B, C23B, C24B,
C25B, C26B, C27B, C28B, C29B, C30B, C31B}
{F16A, F17A, F18A} sigma for 1-2: 0.02, 1-3: 0.04
as
{F16B, F17B, F18B}
{F19A, F20A, F21A} sigma for 1-2: 0.02, 1-3: 0.04
as
{F19B, F20B, F21B}
{F22A, F23A, F24A} sigma for 1-2: 0.02, 1-3: 0.04
as
{F22B, F23B, F24B}
4. Others
 Sof(Mo1B)=Sof(P1B)=Sof(P2B)=Sof(O1B)=Sof(C1B)=Sof(C2B)=Sof(H2B)=Sof(C3B)=
 Sof(H3B)=Sof(C4B)=Sof(C5B)=Sof(H5B)=Sof(C6B)=Sof(H6B)=Sof(C7B)=Sof(C8B)=
 Sof(C9B)=Sof(H9B)=Sof(C10B)=Sof(H10B)=Sof(C11B)=Sof(H11B)=Sof(C12B)=Sof(H12B)=
 Sof(C13B)=Sof(C14B)=Sof(C15B)=Sof(H15B)=Sof(C16B)=Sof(H16B)=Sof(C17B)=
 Sof(H17B)=Sof(C18B)=Sof(H18B)=Sof(C19B)=Sof(H19B)=Sof(C20B)=Sof(H20D)=
 Sof(H20E)=Sof(H20F)=Sof(C21B)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C22B)=
 Sof(H22B)=Sof(C23B)=Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C24B)=Sof(H24D)=
 Sof(H24E)=Sof(H24F)=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)=Sof(C31B)=1-FVAR(1)
 Sof(Mo1A)=Sof(P1A)=Sof(P2A)=Sof(O1A)=Sof(C1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=
 Sof(H3A)=Sof(C4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(C8A)=
 Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10A)=Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(H12A)=
 Sof(C13A)=Sof(C14A)=Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(H16A)=Sof(C17A)=
 Sof(H17A)=Sof(C18A)=Sof(H18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20A)=
 Sof(H20B)=Sof(H20C)=Sof(C21A)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22A)=
 Sof(H22A)=Sof(C23A)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C24A)=Sof(H24A)=
 Sof(H24B)=Sof(H24C)=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)=Sof(C31A)=FVAR(1)
 Sof(F22B)=Sof(F23B)=Sof(F24B)=1-FVAR(2)
 Sof(F22A)=Sof(F23A)=Sof(F24A)=FVAR(2)
 Sof(F16B)=Sof(F17B)=Sof(F18B)=1-FVAR(3)
 Sof(F16A)=Sof(F17A)=Sof(F18A)=FVAR(3)
 Sof(F19B)=Sof(F20B)=Sof(F21B)=1-FVAR(4)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=FVAR(4)
5.a Ternary CH refined with riding coordinates:
 C19A(H19A), C22A(H22A), C25A(H25A), C28A(H28A), C19B(H19B), C22B(H22B),
 C25B(H25B), C28B(H28B)
5.b Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C3A(H3A), C5A(H5A), C6A(H6A), C9A(H9A), C10A(H10A), C11A(H11A),
 C12A(H12A), C15A(H15A), C16A(H16A), C17A(H17A), C18A(H18A), C2B(H2B), C3B(H3B),
  C5B(H5B), C6B(H6B), C9B(H9B), C10B(H10B), C11B(H11B), C12B(H12B), C15B(H15B),
 C16B(H16B), C17B(H17B), C18B(H18B), C33(H33), C34(H34), C35(H35), C41(H41),
 C42(H42), C43(H43), C49(H49), C50(H50), C51(H51), C57(H57), C58(H58), C59(H59),
  C64(H64), C65(H65), C66(H66), C67(H67), C68(H68), C69(H69), C70(H70),
 C71(H71), C72(H72), C73(H73), C74(H74), C75(H75)
5.c Idealised Me refined as rotating group:
 C20A(H20A,H20B,H20C), C21A(H21A,H21B,H21C), C23A(H23A,H23B,H23C), C24A(H24A,
 H24B,H24C), C26A(H26A,H26B,H26C), C27A(H27A,H27B,H27C), C29A(H29A,H29B,H29C),
 C30A(H30A,H30B,H30C), C20B(H20D,H20E,H20F), C21B(H21D,H21E,H21F), C23B(H23D,
 H23E,H23F), C24B(H24D,H24E,H24F), C26B(H26D,H26E,H26F), C27B(H27D,H27E,H27F),
 C29B(H29D,H29E,H29F), C30B(H30D,H30E,H30F)
;
_olex2_submission_special_instructions 'No special instructions were received'