Terminal methylene phosphonium ions: precursors for transient monosubstituted phosphinocarbenes.
Löwe, Pawel; Wünsche, Marius A; Purtscher, Felix R. S.; Gamper, Jakob; Hofer, Thomas S.; Wilm, Lukas F. B.; Röthel, Maike B; Dielmann, Fabian; Chemical science 14 (2023) 7928–7935; doi:10.1039/d3sc02899b

data_1569382
_publ_section_title
;
 Terminal methylene phosphonium ions: precursors for transient
 monosubstituted phosphinocarbenes.
;
_journal_issue                   29
_journal_name_full               'Chemical science'
_journal_page_first              7928
_journal_page_last               7935
_journal_paper_doi               10.1039/d3sc02899b
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C23 H47 N6 P'
_chemical_formula_sum            'C23 H47 N6 P'
_chemical_formula_weight         438.63
_chemical_name_systematic        (sItBuN)2PMe
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-03-10
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-02-23 deposited with the CCDC.	2023-06-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.6430(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.9856(3)
_cell_length_b                   9.8313(2)
_cell_length_c                   20.5049(5)
_cell_measurement_reflns_used    9696
_cell_measurement_temperature    100
_cell_measurement_theta_max      29.57
_cell_measurement_theta_min      2.31
_cell_volume                     2563.90(10)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2013/4 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0326
_diffrn_reflns_av_unetI/netI     0.0194
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            41012
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.574
_diffrn_reflns_theta_min         2.028
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.128
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8442
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1262 before and 0.0550 after correction.
The Ratio of minimum to maximum transmission is 0.8442.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.136
_exptl_crystal_description       block
_exptl_crystal_F_000             968
_exptl_crystal_preparation       'via EXP PL790'
_exptl_crystal_recrystallization_method
'crystallized out of a concentrated n-hexane solution at room temperature'
_exptl_crystal_size_max          0.742
_exptl_crystal_size_mid          0.589
_exptl_crystal_size_min          0.442
_refine_diff_density_max         0.483
_refine_diff_density_min         -0.376
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.157
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     294
_refine_ls_number_reflns         7191
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.157
_refine_ls_R_factor_all          0.0399
_refine_ls_R_factor_gt           0.0388
_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^)+(0.0557P)^2^+0.6406P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1018
_refine_ls_wR_factor_ref         0.1026
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6885
_reflns_number_total             7191
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02899b2.cif
_cod_data_source_block           p21c_a
_cod_depositor_comments
'Adding full bibliography for 1569380--1569388.cif.'
_cod_database_code               1569382
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.946
_shelx_estimated_absorpt_t_min   0.911
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Others
 Sof(H1BD)=Sof(H1BE)=Sof(H1BF)=Sof(P1B)=1-FVAR(1)
 Sof(P1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=FVAR(1)
3.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C3(H3A,H3B), C7(H7A,H7B), C6(H6A,H6B)
3.b Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C23(H23A,H23B,H23C), C14(H14A,H14B,H14C), C11(H11A,H11B,
 H11C), C13(H13A,H13B,H13C), C18(H18A,H18B,H18C), C15(H15A,H15B,H15C), C21(H21A,
 H21B,H21C), C19(H19A,H19B,H19C), C17(H17A,H17B,H17C), C9(H9A,H9B,H9C),
 C22(H22A,H22B,H22C), C1(H1AA,H1AB,H1AC), C1(H1BD,H1BE,H1BF)
;
_shelx_res_checksum              40286
_shelx_hkl_checksum              72236
_olex2_exptl_crystal_mounting_method 'mounted on glass capillary'
_olex2_submission_original_sample_id PL790
_olex2_submission_special_instructions 'No special instructions were received'