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_4132734
_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
'C60 H80 Mo2 N2 P4, C6 H5 Cl, 2(C32 H12 B F24)'
_chemical_formula_sum            'C130 H109 B2 Cl F48 Mo2 N2 P4'
_chemical_formula_weight         2984.02
_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             2018-05-29
_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                65.959(2)
_cell_angle_beta                 81.517(2)
_cell_angle_gamma                78.563(2)
_cell_formula_units_Z            1
_cell_length_a                   13.0558(8)
_cell_length_b                   16.4548(10)
_cell_length_c                   16.5050(10)
_cell_measurement_reflns_used    9612
_cell_measurement_temperature    100
_cell_measurement_theta_max      39.11
_cell_measurement_theta_min      2.27
_cell_volume                     3165.1(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker-AXS, 2007)'
_computing_data_collection       'APEX2 v2014.11-0 (Bruker-AXS, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker-AXS, 2007)'
_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                 'CMOS Area Detector'
_diffrn_detector_area_resol_mean 10.24
_diffrn_detector_type            'Bruker PHOTON 100 CMOS'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.962
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'multilayer mirrors'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0460
_diffrn_reflns_av_unetI/netI     0.0463
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            204504
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         39.996
_diffrn_reflns_theta_min         2.410
_diffrn_source                   'I\mS HB micro-focus sealed tube'
_diffrn_source_current           1
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatech I\mS HB'
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.392
_exptl_absorpt_correction_T_max  0.7479
_exptl_absorpt_correction_T_min  0.7062
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0939 before and 0.0516 after correction. The Ratio of minimum to maximum transmission is 0.9442. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.566
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1506
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.12
_refine_diff_density_max         5.876
_refine_diff_density_min         -0.902
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1207
_refine_ls_number_reflns         38344
_refine_ls_number_restraints     1510
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0924
_refine_ls_R_factor_gt           0.0557
_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^)+(0.0708P)^2^+2.4928P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1344
_refine_ls_wR_factor_ref         0.1540
_reflns_Friedel_coverage         0.000
_reflns_number_gt                27149
_reflns_number_total             38344
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b05874_si_001.cif
_cod_data_source_block           7
_cod_database_code               4132734
_shelxl_version_number           2014-7
_shelx_estimated_absorpt_t_max   0.954
_shelx_estimated_absorpt_t_min   0.872
_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
 B1, C31, C32, C33, C34, C35, C36A, F1A, F2A, F3A, C36B, F1B, F2B, F3B, C37,
 C38A, F4A, F5A, F6A, C38B, F4B, F5B, F6B, C39, C40, C41, C42, C43, C44, F7A,
 F8A, F9A, F7B, F8B, F9B, C45, C46, F10A, F11A, F12A, F10B, F11B, F12B, F10C,
 F11C, F12C, C47, C48, C49, C50, C51, C52, F13A, F14A, F15A, F13B, F14B, F15B,
 C53, C54A, F16A, F17A, F18A, C54B, F16B, F17B, F18B, C55, C56, C57A, C57B,
 C58A, C58B, C59, C60, F19A, F20A, F21A, F19B, F20B, F21B, C61A, C62A, F22A,
 F23A, F24A, C61B, C62B, F22B, F23B, F24B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Same fragment restrains
{C35, C36A, F3A, F2A, F1A} sigma for 1-2: 0.02, 1-3: 0.04
{C35, C36B, F1B, F2B, F3B} sigma for 1-2: 0.02, 1-3: 0.04
as
{C35, C36A, F1A, F2A, F3A}
{C35, C36A, F1A, F2A, F3A, C36B, F1B, F2B, F3B} sigma for 1-2: 0.02, 1-3: 0.04
as
{C37, C38A, F4A, F5A, F6A, C38B, F4B, F5B, F6B}
{C43, C44, F9A, F8A, F7A} sigma for 1-2: 0.02, 1-3: 0.04
{C43, C44, F7B, F8B, F9B} sigma for 1-2: 0.02, 1-3: 0.04
as
{C43, C44, F7A, F8A, F9A}
{C45, C46, F12A, F11A, F10A} sigma for 1-2: 0.02, 1-3: 0.04
{C45, C46, F10C, F11C, F12C} sigma for 1-2: 0.02, 1-3: 0.04
{C45, C46, F10B, F11B, F12B} sigma for 1-2: 0.02, 1-3: 0.04
as
{C45, C46, F10A, F11A, F12A}
{C43, C44, F7A, F8A, F9A, F7B, F8B, F9B} sigma for 1-2: 0.02, 1-3: 0.04
as
{C51, C52, F13A, F14A, F15A, F13B, F14B, F15B}
{C36A, F1A, F2A, F3A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C54A, F16A, F17A, F18A}
{C36A, F1A, F2A, F3A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C54B, F16B, F17B, F18B}
{C43, C44, F7A, F8A, F9A, F7B, F8B, F9B} sigma for 1-2: 0.02, 1-3: 0.04
as
{C59, C60, F19A, F20A, F21A, F19B, F20B, F21B}
{C43, C44, F7A, F8A, F9A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C61A, C62A, F22A, F23A, F24A}
{C43, C44, F7A, F8A, F9A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C61B, C62B, F22B, F23B, F24B}
4. Others
 1*[Sof(F10A)+Sof(F11A)+Sof(F12A)]+1*[Sof(F10B)+Sof(F11B)+Sof(F12B)]+1*
 [Sof(F10C)+Sof(F11C)+Sof(F12C)]=1 with esd of 0
 1*[Sof(F10A)+Sof(F11A)+Sof(F12A)]+1*[Sof(F10B)+Sof(F11B)+Sof(F12B)]+1*
 [Sof(F10C)+Sof(F11C)+Sof(F12C)]=1 with esd of 0
 Sof(C36B)=Sof(F1B)=Sof(F2B)=Sof(F3B)=1-FVAR(1)
 Sof(C36A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=FVAR(1)
 Sof(C38B)=Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(2)
 Sof(C38A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=FVAR(2)
 Sof(F7B)=Sof(F8B)=Sof(F9B)=1-FVAR(3)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=FVAR(3)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=FVAR(4)
 Sof(F10B)=Sof(F11B)=Sof(F12B)=FVAR(5)
 Sof(F10C)=Sof(F11C)=Sof(F12C)=FVAR(6)
 Sof(F13B)=Sof(F14B)=Sof(F15B)=1-FVAR(7)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=FVAR(7)
 Sof(C54B)=Sof(F16B)=Sof(F17B)=Sof(F18B)=1-FVAR(8)
 Sof(C54A)=Sof(F16A)=Sof(F17A)=Sof(F18A)=FVAR(8)
 Sof(F19B)=Sof(F20B)=Sof(F21B)=1-FVAR(9)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=FVAR(9)
 Sof(C57B)=Sof(H57B)=Sof(C58B)=Sof(H58B)=Sof(C61B)=Sof(C62B)=Sof(F22B)=
 Sof(F23B)=Sof(F24B)=1-FVAR(10)
 Sof(C57A)=Sof(H57A)=Sof(C58A)=Sof(H58A)=Sof(C61A)=Sof(C62A)=Sof(F22A)=
 Sof(F23A)=Sof(F24A)=FVAR(10)
 Fixed Sof: Cl1(0.5) C63(0.5) C64(0.5) H64(0.5) C65(0.5) H65(0.5) C66(0.5)
 H66(0.5) C67(0.5) H67(0.5) C68(0.5) H68(0.5)
5.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C19(H19), C22(H22), C25(H25), C28(H28)
5.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C15(H15), C16(H16), C17(H17), C18(H18),
 C64(H64), C65(H65), C66(H66), C67(H67), C68(H68), C32(H32), C33(H33), C34(H34),
  C40(H40), C41(H41), C42(H42), C48(H48), C49(H49), C50(H50), C56(H56),
 C57A(H57A), C57B(H57B), C58A(H58A), C58B(H58B)
5.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C)
;
_olex2_submission_special_instructions 'No special instructions were received'