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_4132730
_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         'C31 H40 Mo O2 P2, 2(C3 H3)'
_chemical_formula_sum            'C37 H46 Mo O2 P2'
_chemical_formula_weight         680.62
_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             2014-11-29
_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                93.575(10)
_cell_angle_beta                 98.963(9)
_cell_angle_gamma                103.528(10)
_cell_formula_units_Z            2
_cell_length_a                   8.773(3)
_cell_length_b                   11.504(3)
_cell_length_c                   16.681(5)
_cell_measurement_reflns_used    4285
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      24.08
_cell_measurement_theta_min      2.43
_cell_volume                     1608.2(8)
_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 0.883
_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  0.1450
_diffrn_reflns_av_unetI/netI     0.1491
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.883
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            41979
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.883
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         28.726
_diffrn_reflns_theta_min         1.830
_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    0.540
_exptl_absorpt_correction_T_max  0.9878
_exptl_absorpt_correction_T_min  0.8570
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1093 before and 0.0977 after correction.
The Ratio of minimum to maximum transmission is 0.8676.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.405
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             712
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.581
_refine_diff_density_min         -1.819
_refine_diff_density_rms         0.153
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     400
_refine_ls_number_reflns         7362
_refine_ls_number_restraints     8
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.1364
_refine_ls_R_factor_gt           0.0719
_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^)+(0.0879P)^2^+1.0535P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1592
_refine_ls_wR_factor_ref         0.1853
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4591
_reflns_number_total             7362
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b05874_si_001.cif
_cod_data_source_block           2
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_crystal_density_meas' value 'not measured' was
changed to '?' -- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 6909 2019-04-08 15:41:33Z antanas 
;
_cod_original_cell_volume        1608.3(8)
_cod_database_code               4132730
_shelxl_version_number           2014-7
_shelx_estimated_absorpt_t_max   0.984
_shelx_estimated_absorpt_t_min   0.943
_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
 O1A, C31A, O2B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
O1A \\sim C31A \\sim O2B: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
4. Same fragment restrains
{C31B, O1B, O1A} sigma for 1-2: 0.01, 1-3: 0.04
as
{O2A, C31A, O2B}
5. Others
 Sof(C31B)=Sof(O1B)=Sof(O2B)=1-FVAR(1)
 Sof(O1A)=Sof(O2A)=Sof(C31A)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C19(H19), C20(H20), C25(H25), C26(H26)
6.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), C32(H32), C33(H33), C34(H34), C35(H35),
  C36(H36), C37(H37)
6.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C)
;
_olex2_submission_special_instructions 'No special instructions were received'