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_4518852
_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         'C36 H33 Cl O P3 Pt, C F3 O3 S, C H2 Cl2'
_chemical_formula_sum            'C38 H35 Cl3 F3 O4 P3 Pt S'
_chemical_formula_weight         1039.07
_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             2019-12-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                102.068(4)
_cell_angle_beta                 96.510(4)
_cell_angle_gamma                93.444(4)
_cell_formula_units_Z            4
_cell_length_a                   11.1267(13)
_cell_length_b                   13.0225(15)
_cell_length_c                   28.766(4)
_cell_measurement_reflns_used    9467
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.43
_cell_measurement_theta_min      2.34
_cell_volume                     4034.6(9)
_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  'XL (Sheldrick, 2008)'
_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 0.997
_diffrn_measured_fraction_theta_max 0.995
_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  0.0696
_diffrn_reflns_av_unetI/netI     0.0813
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            56331
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.450
_diffrn_reflns_theta_min         2.074
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.900
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.5155
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1212 before and 0.0768 after correction. The Ratio of minimum to maximum transmission is 0.6915. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.711
_exptl_crystal_description       block
_exptl_crystal_F_000             2048
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.34
_exptl_crystal_size_min          0.28
_refine_diff_density_max         2.621
_refine_diff_density_min         -2.523
_refine_diff_density_rms         0.201
_refine_ls_extinction_coef       0.00047(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     993
_refine_ls_number_reflns         18361
_refine_ls_number_restraints     114
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0792
_refine_ls_R_factor_gt           0.0558
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0259P)^2^+43.7699P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1163
_refine_ls_wR_factor_ref         0.1250
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14439
_reflns_number_total             18361
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c02254_si_004.cif
_cod_data_source_block           cxy1037_0m
_cod_depositor_comments
'Adding full bibliography for 4518848--4518852.cif.'
_cod_database_code               4518852
_shelx_shelxl_version_number     2016/6
_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
 S3-O10 = S3-O9 = S3-O11 = S2-O7 = S2-O6 = S2-O8
 1.44 with sigma of 0.02
 F7-C77 = F9-C77 = F8-C77 = F6-C76 = F4-C76 = F5-C76
 1.34 with sigma of 0.02
 S3-C77 = S2-C76
 1.83 with sigma of 0.02
 Cl3A-C73A = Cl4A-C73A = Cl4-C73 = Cl3-C73
 1.79 with sigma of 0.02
 O9-O10 = O6-O8
 2.44 with sigma of 0.04
 O10-O11 = O8-O7
 2.44 with sigma of 0.04
 O11-O9 = O7-O6
 2.44 with sigma of 0.04
 F9-F8 = F6-F4
 2.14 with sigma of 0.04
 F6-F5 = F8-F7
 2.14 with sigma of 0.04
 F5-F4 = F9-F7
 2.14 with sigma of 0.04
 C76-O8 = C77-O10
 2.56 with sigma of 0.04
 C76-O6 = O9-C77
 2.56 with sigma of 0.04
 O11-C77 = C76-O7
 2.56 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O6 \\sim S2 \\sim O7 \\sim O8 \\sim C76 \\sim F4 \\sim F5 \\sim F6: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
Cl3 \\sim C73 \\sim Cl4: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(O7) \\sim Ueq, Uanis(S3) \\sim Ueq, Uanis(F4) \\sim Ueq, Uanis(F5) \\sim
Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O9) = Uanis(O6)
Uanis(O10) = Uanis(O8)
Uanis(S2) = Uanis(S3)
Uanis(O7) = Uanis(O11)
Uanis(F5) = Uanis(F8)
Uanis(F4) = Uanis(F9)
Uanis(F7) = Uanis(F6)
Uanis(C77) = Uanis(C76)
Uanis(Cl3) = Uanis(Cl3A)
Uanis(C73) = Uanis(C73A)
Uanis(Cl4) = Uanis(Cl4A)
4. Others
 Sof(Cl3A)=Sof(C73A)=Sof(H73C)=Sof(H73D)=Sof(Cl4A)=1-FVAR(1)
 Sof(Cl3)=Sof(Cl4)=Sof(C73)=Sof(H73A)=Sof(H73B)=FVAR(1)
 Fixed Sof: S2(0.6222) F4(0.6222) F5(0.6222) F6(0.6222) O6(0.6222) O7(0.6222)
 O8(0.6222) C76(0.6222) S3(0.3778) F7(0.3778) F8(0.3778) F9(0.3778) O9(0.3778)
 O10(0.3778) O11(0.3778) C77(0.3778)
5.a Secondary CH2 refined with riding coordinates:
 C73(H73A,H73B), C74(H74A,H74B), C73A(H73C,H73D)
5.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C18(H18), C32(H32), C13(H13), C33(H33), C20(H20), C19(H19), C22(H22),
 C17(H17), C23(H23), C15(H15), C14(H14), C34(H34), C29(H29), C10(H10), C28(H28),
  C16(H16), C9(H9), C8(H8), C26(H26), C36(H36), C35(H35), C30(H30), C24(H24),
 C11(H11), C27(H27), C63(H63), C62(H62), C64(H64), C65(H65), C43(H43), C60(H60),
  C44(H44), C71(H71), C68(H68), C69(H69), C72(H72), C59(H59), C66(H66),
 C45(H45), C70(H70), C51(H51), C49(H49), C52(H52), C50(H50), C58(H58), C46(H46),
  C53(H53), C47(H47), C54(H54), C56(H56), C55(H55)
5.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C)
5.d Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2)
;
_olex2_submission_special_instructions 'No special instructions were received'