Dicationic phosphonium salts: Lewis acid initiators for the Mukaiyama-aldol reaction
Barrado, Alejandro G.; Bayne, Julia M.; Johnstone, Timothy C.; Lehmann, Christian W.; Stephan, Douglas W.; Alcarazo, Manuel; Dalton Transactions  (2017) –; doi:10.1039/C7DT03197A

data_7044759
_publ_section_title
;
 Dicationic phosphonium salts: Lewis acid initiators for the
 Mukaiyama-aldol reaction
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/C7DT03197A
_journal_year                    2017
_chemical_compound_source        dichloromethane,pentane
_chemical_formula_moiety         '2(C H2 Cl2), 2(C33 H43 N2 P), 4(B F4)'
_chemical_formula_sum            'C68 H90 B4 Cl4 F16 N4 P2'
_chemical_formula_weight         1514.41
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_block_code                HOS-HH-111-03
_audit_creation_date             2017-10-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5375)
;
_audit_update_record
;
2017-10-29 deposited with the CCDC.
2017-11-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.330(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.675(3)
_cell_length_b                   15.547(3)
_cell_length_c                   25.725(4)
_cell_measurement_reflns_used    9770
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.79
_cell_measurement_theta_min      2.19
_cell_volume                     7437(2)
_computing_cell_refinement       'SAINT software (Bruker AXS, 2004)'
_computing_data_collection       'APEX2 (Bruker AXS, 2008)'
_computing_data_reduction        'SAINT software (Bruker AXS, 2004)'
_computing_molecular_graphics    'DIAMOND (Crystal Impact GbR, 2005)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-97 (G. M. Sheldrick, 2008)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 66.67
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'CCD \f and \w scans'
_diffrn_radiation_monochromator  'Incoatec Helios mirrors'
_diffrn_radiation_source         '0.2 x 2mm^2^ focus rotating anode'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0748
_diffrn_reflns_av_unetI/netI     0.0391
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            208223
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.498
_diffrn_reflns_theta_min         1.292
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.285
_exptl_absorpt_correction_T_max  0.99053
_exptl_absorpt_correction_T_min  0.97150
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
SADABS-2009/1 (Bruker,2010) was used for absorption correction.
wR2(int) was 0.1312 before and 0.0566 after correction.
The Ratio of minimum to maximum transmission is 0.9037.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.353
_exptl_crystal_description       prism
_exptl_crystal_F_000             3152
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.626
_refine_diff_density_min         -1.239
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     982
_refine_ls_number_reflns         22623
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.1068
_refine_ls_R_factor_gt           0.0727
_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^)+(0.0770P)^2^+14.2381P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1778
_refine_ls_wR_factor_ref         0.2013
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15874
_reflns_number_total             22623
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt03197a2.cif
_cod_data_source_block           8326sadabs
_cod_database_code               7044759
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.975
_shelx_estimated_absorpt_t_min   0.916
_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
2. Restrained distances
 Cl4C-C99C = Cl4A-C99A = Cl3C-C99C = Cl3A-C99A
 1.74 with sigma of 0.001
3. Others
 Sof(C50B)=Sof(H50B)=Sof(C51B)=Sof(H51D)=Sof(H51E)=Sof(H51F)=Sof(C52B)=
 Sof(H52D)=Sof(H52E)=Sof(H52F)=Sof(C53A)=Sof(H53A)=Sof(C54A)=Sof(H54A)=
 Sof(H54B)=Sof(H54C)=Sof(C55A)=Sof(H55A)=Sof(H55B)=Sof(H55C)=1-FVAR(1)
 Sof(C50A)=Sof(H50A)=Sof(C51A)=Sof(H51A)=Sof(H51B)=Sof(H51C)=Sof(C52A)=
 Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C53B)=Sof(H53B)=Sof(C54B)=Sof(H54D)=
 Sof(H54E)=Sof(H54F)=Sof(C55B)=Sof(H55D)=Sof(H55E)=Sof(H55F)=FVAR(1)
 Fixed Sof: Cl3A(0.33333) Cl3B(0.33333) Cl3C(0.33333) Cl4A(0.33333)
 Cl4B(0.33333) Cl4C(0.33333) F6A(0.33333) F6B(0.33333) F6C(0.33333)
 F7A(0.33333) F7B(0.33333) F7C(0.33333) F8A(0.33333) F8B(0.33333) F8C(0.33333)
 F9A(0.5) F9B(0.5) F10A(0.5) F10B(0.5) F12A(0.5) F12B(0.5) F13A(0.33333)
 F13B(0.33333) F13C(0.33333) F14A(0.33333) F14B(0.33333) F14C(0.33333)
 F15A(0.33333) F15B(0.33333) F15C(0.33333) C99A(0.33333) H99A(0.33333)
 H99B(0.33333) C99B(0.33333) H99C(0.33333) H99D(0.33333) C99C(0.33333)
 H99E(0.33333) H99F(0.33333)
4.a Ternary CH refined with riding coordinates:
 C4(H4), C7(H7), C10(H10), C13(H13), C44(H44), C47(H47), C50A(H50A),
 C50B(H50B), C53A(H53A), C53B(H53B)
4.b Secondary CH2 refined with riding coordinates:
 C98(H98A,H98B), C99A(H99A,H99B), C99B(H99C,H99D), C99C(H99E,H99F)
4.c Aromatic/amide H refined with riding coordinates:
 C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C23(H23), C24(H24),
 C25(H25), C26(H26), C27(H27), C29(H29), C30(H30), C31(H31), C32(H32), C33(H33),
  C57(H57), C58(H58), C59(H59), C60(H60), C61(H61), C63(H63), C64(H64),
 C65(H65), C66(H66), C67(H67), C69(H69), C70(H70), C71(H71), C72(H72), C73(H73)
4.d Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C11(H11A,
 H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C),
 C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C48(H48A,H48B,H48C), C49(H49A,H49B,
 H49C), C51A(H51A,H51B,H51C), C51B(H51D,H51E,H51F), C52A(H52A,H52B,H52C),
 C52B(H52D,H52E,H52F), C54A(H54A,H54B,H54C), C54B(H54D,H54E,H54F), C55A(H55A,
 H55B,H55C), C55B(H55D,H55E,H55F)
;
_shelx_res_checksum              54879
_olex2_submission_special_instructions 'No special instructions were received'