Hydration of Cyanohydrins by Highly Active Cationic Pt Catalysts: Mechanism and Scope
Li, Chengcheng; Chang, Xiao-Yong; Huo, Luqiong; Tan, Haibo; Xing, Xiangyou; Xu, Chen; ACS Catalysis 11 (2021) 8716–8726; doi:10.1021/acscatal.1c02254

data_4518848
_publ_section_title
;
 Hydration of Cyanohydrins by Highly Active Cationic Pt Catalysts:
 Mechanism and Scope
;
_journal_issue                   14
_journal_name_full               'ACS Catalysis'
_journal_page_first              8716
_journal_page_last               8726
_journal_paper_doi               10.1021/acscatal.1c02254
_journal_volume                  11
_journal_year                    2021
_chemical_formula_moiety         'C33 H33 Cl O7 P3 Pt, C F3 O3 S, C H2 Cl2'
_chemical_formula_sum            'C35 H35 Cl3 F3 O10 P3 Pt S'
_chemical_formula_weight         1099.04
_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     dual
_audit_creation_date             2019-11-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                112.381(2)
_cell_angle_beta                 115.776(2)
_cell_angle_gamma                90.585(2)
_cell_formula_units_Z            4
_cell_length_a                   17.1276(12)
_cell_length_b                   17.7163(12)
_cell_length_c                   17.8919(13)
_cell_measurement_reflns_used    9792
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.38
_cell_measurement_theta_min      2.32
_cell_volume                     4418.7(6)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 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      100
_diffrn_detector                 'Bruker PHOTON 100 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'BrukerD8 venture microsource'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0657
_diffrn_reflns_av_unetI/netI     0.0722
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            60103
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.408
_diffrn_reflns_theta_min         2.224
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.576
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.3919
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1545 before and 0.0928 after correction. The Ratio of minimum to maximum transmission is 0.5255. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.652
_exptl_crystal_description       block
_exptl_crystal_F_000             2168
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.16
_refine_diff_density_max         4.077
_refine_diff_density_min         -3.171
_refine_diff_density_rms         0.235
_refine_ls_extinction_coef       0.00033(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1064
_refine_ls_number_reflns         22002
_refine_ls_number_restraints     128
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0787
_refine_ls_R_factor_gt           0.0593
_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^)+(0.0678P)^2^+43.3372P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1527
_refine_ls_wR_factor_ref         0.1675
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17274
_reflns_number_total             22002
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c02254_si_003.cif
_cod_data_source_block           cxy1018_0m
_cod_depositor_comments
'Adding full bibliography for 4518848--4518852.cif.'
_cod_original_cell_volume        4418.7(5)
_cod_database_code               4518848
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.598
_shelx_estimated_absorpt_t_min   0.394
_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, All O(H) groups
2. Restrained distances
 Cl7A-C73 = Cl7-C73 = Cl8-C72 = Cl8A-C72
 1.79 with sigma of 0.02
 Cl3-C67 = Cl4-C67
 1.79 with sigma of 0.02
 Cl7-Cl7A = Cl8-Cl8A
 2.9 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C72 \\sim Cl8 \\sim Cl8A \\sim Cl7 \\sim C73 \\sim Cl7A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02
C67 \\sim Cl3 \\sim Cl4: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C58A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl8) \\sim Ueq, Uanis(Cl7) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(Cl7) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(Cl7A) \\sim Ueq, Uanis(Cl8)
\\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(Cl8A) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(Cl3) \\sim Ueq, Uanis(C67) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C45) = Uanis(C45A)
Uanis(C58) = Uanis(C58A)
Uanis(C72) = Uanis(C73)
Uanis(Cl7) = Uanis(Cl8)
Uanis(Cl8A) = Uanis(Cl7A)
Uanis(Cl4) = Uanis(Cl3)
4. Others
 Sof(C45A)=Sof(H45D)=Sof(H45E)=Sof(H45F)=1-FVAR(1)
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=FVAR(1)
 Sof(C58A)=Sof(H58D)=Sof(H58E)=Sof(H58F)=1-FVAR(2)
 Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=FVAR(2)
 Fixed Sof: Cl3(0.5) Cl4(0.5) C67(0.5) H67A(0.5) H67B(0.5) Cl7(0.25) Cl8(0.25)
 C73(0.25) H73A(0.25) H73B(0.25) C72(0.25) H72A(0.25) H72B(0.25) Cl7A(0.25)
 Cl8A(0.25)
5.a Secondary CH2 refined with riding coordinates:
 C62(H62A,H62B), C29(H29A,H29B), C67(H67A,H67B), C68(H68A,H68B), C73(H73A,
 H73B), C72(H72A,H72B)
5.b Aromatic/amide H refined with riding coordinates:
 C57(H57), C52(H52), C39(H39), C44(H44), C56(H56), C60(H60), C59(H59),
 C38(H38), C43(H43), C66(H66), C51(H51), C65(H65), C24(H24), C6(H6), C23(H23),
 C26(H26), C27(H27), C11(H11), C32(H32), C10(H10), C19(H19), C5(H5), C18(H18),
 C33(H33)
5.c Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C53(H53A,H53B,H53C), C45(H45A,H45B,H45C), C35(H35A,H35B,
 H35C), C40(H40A,H40B,H40C), C58(H58A,H58B,H58C), C1(H1A,H1B,H1C), C25(H25A,
 H25B,H25C), C12(H12A,H12B,H12C), C2(H2A,H2B,H2C), C20(H20A,H20B,H20C), C7(H7A,
 H7B,H7C), C45A(H45D,H45E,H45F), C58A(H58D,H58E,H58F)
5.d Idealised tetrahedral OH refined as rotating group:
 O8(H8), O1(H1)
;
_olex2_submission_special_instructions 'No special instructions were received'