Isolation of singlet carbene derived 2-phospha-1,3-butadienes and their sequential one-electron oxidation to radical cations and dications
Sharma, Mahendra K.; Blomeyer, Sebastian; Glodde, Timo; Neumann, Beate; Stammler, Hans-Georg; Hinz, Alexander; van Gastel, Maurice; Ghadwal, Rajendra S.; Chemical Science 11 (2020) 1975–1984; doi:10.1039/C9SC05598C

data_1557449
_publ_section_title
;
 Isolation of singlet carbene derived 2-phospha-1,3-butadienes and their
 sequential one-electron oxidation to radical cations and dications
;
_journal_issue                   7
_journal_name_full               'Chemical Science'
_journal_page_first              1975
_journal_page_last               1984
_journal_paper_doi               10.1039/C9SC05598C
_journal_volume                  11
_journal_year                    2020
_chemical_formula_moiety         'C54 H72 Cl N3 P, C F3 O3 S'
_chemical_formula_sum            'C55 H72 Cl F3 N3 O3 P S'
_chemical_formula_weight         978.63
_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             2019-07-01
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2019-08-28 deposited with the CCDC.	2020-01-06 downloaded from the CCDC.
;
_cell_angle_alpha                98.063(2)
_cell_angle_beta                 91.131(2)
_cell_angle_gamma                103.315(3)
_cell_formula_units_Z            2
_cell_length_a                   11.0592(4)
_cell_length_b                   12.9006(3)
_cell_length_c                   18.7834(5)
_cell_measurement_reflns_used    21348
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.2750
_cell_measurement_theta_min      3.4950
_cell_volume                     2578.25(14)
_computing_cell_refinement       'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3114
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -60.00  29.00   1.00   12.50    --  -38.50  57.00  30.00   89
  2  \w    -58.00  33.00   1.00   12.50    --  -38.50  38.00 -60.00   91
  3  \w    -50.00  31.00   1.00   12.50    --  -38.50  77.00 150.00   81
  4  \w    -66.00 -18.00   1.00   12.50    --  -38.50 -38.00 -30.00   48
  5  \w     19.00  74.00   1.00   12.50    --   42.70  57.00 150.00   55
  6  \w      3.00  75.00   1.00   12.50    --   42.70 -99.00 -90.00   72
  7  \w     15.00  43.00   1.00   12.50    --   42.70  77.00 120.00   28
  8  \w     65.00 108.00   1.00   12.50    --   42.70  77.00 120.00   43
  9  \w     15.00  52.00   1.00   12.50    --   42.70  77.00   0.00   37
 10  \w     20.00  96.00   1.00   12.50    --   42.70  57.00  30.00   76
 11  \w     10.00  67.00   1.00   12.50    --   42.70 -99.00  90.00   57
 12  \w     17.00  61.00   1.00   12.50    --   42.70  77.00-180.00   44
 13  \w     13.00  60.00   1.00   12.50    --   42.70  77.00 -60.00   47
 14  \w     64.00 114.00   1.00   12.50    --   42.70  77.00-180.00   50
 15  \w     13.00 114.00   1.00   12.50    --   42.70  77.00-120.00  101
 16  \w     29.00  57.00   1.00   12.50    --   42.70  38.00   0.00   28
 17  \w     13.00  80.00   1.00   12.50    --   42.70  77.00  60.00   67
 18  \w     31.00  89.00   1.00   49.50    --  111.00 -94.00   0.00   58
 19  \w     81.00 177.00   1.00   49.50    --  111.00  77.00 -30.00   96
 20  \w     41.00 102.00   1.00   49.50    --  111.00-125.00 -30.00   61
 21  \w     43.00 137.00   1.00   49.50    --  111.00 -61.00 150.00   94
 22  \w     81.00 108.00   1.00   49.50    --  111.00  77.00  90.00   27
 23  \w     81.00 176.00   1.00   49.50    --  111.00  77.00 150.00   95
 24  \w     81.00 164.00   1.00   49.50    --  111.00  77.00-120.00   83
 25  \w     85.00 130.00   1.00   49.50    --  111.00  61.00-120.00   45
 26  \w     85.00 177.00   1.00   49.50    --  111.00  61.00 -60.00   92
 27  \w     83.00 110.00   1.00   49.50    --  111.00  68.00 -51.76   27
 28  \w     85.00 178.00   1.00   49.50    --  111.00  62.00  93.47   93
 29  \w    112.00 146.00   1.00   49.50    --  111.00  77.00  60.00   34
 30  \w     81.00 171.00   1.00   49.50    --  111.00  77.00  30.00   90
 31  \w     85.00 112.00   1.00   49.50    --  111.00  61.00  30.00   27
 32  \w     81.00 107.00   1.00   49.50    --  111.00  77.00  60.00   26
 33  \w     43.00 121.00   1.00   49.50    --  111.00-129.00 143.00   78
 34  \w     85.00 112.00   1.00   49.50    --  111.00  61.00  90.00   27
 35  \w     31.00 106.00   1.00   49.50    --  111.00 -94.00 150.00   75
 36  \w     88.00 152.00   1.00   49.50    --  111.00  48.00-154.30   64
 37  \w     81.00 175.00   1.00   49.50    --  111.00  77.00   0.00   94
 38  \w     82.00 108.00   1.00   49.50    --  111.00  77.00-180.00   26
 39  \w     85.00 112.00   1.00   49.50    --  111.00  61.00 120.00   27
 40  \w     81.00 107.00   1.00   49.50    --  111.00  77.00 -90.00   26
 41  \w     91.00 116.00   1.00   49.50    --  111.00-125.00 -90.00   25
 42  \w     81.00 151.00   1.00   49.50    --  111.00  77.00 120.00   70
 43  \w     85.00 111.00   1.00   49.50    --  111.00  61.00  60.00   26
 44  \w     85.00 111.00   1.00   49.50    --  111.00  61.00 150.00   26
 45  \w     81.00 107.00   1.00   49.50    --  111.00  77.00-150.00   26
 46  \w     85.00 111.00   1.00   49.50    --  111.00  61.00-150.00   26
 47  \w     85.00 112.00   1.00   49.50    --  111.00  61.00   0.00   27
 48  \w     85.00 122.00   1.00   49.50    --  111.00  61.00 -30.00   37
 49  \w     45.00 118.00   1.00   49.50    --  111.00-125.00  90.00   73
 50  \w     85.00 112.00   1.00   49.50    --  111.00  61.00 -90.00   27
 51  \w     85.00 112.00   1.00   49.50    --  111.00  61.00-180.00   27
 52  \w     88.00 118.00   1.00   49.50    --  111.00-125.00   0.00   30
 53  \w     58.00  87.00   1.00   49.50    --  111.00-125.00   0.00   29
 54  \w     82.00 178.00   1.00   49.50    --  111.00  73.00-158.66   96
 55  \w     84.00 157.00   1.00   49.50    --  111.00  66.00 -84.59   73
 56  \w     83.00 107.00   1.00   49.50    --  111.00  68.00 120.11   24
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0018531000
_diffrn_orient_matrix_UB_12      -0.0171295000
_diffrn_orient_matrix_UB_13      -0.0828872000
_diffrn_orient_matrix_UB_21      -0.0136864000
_diffrn_orient_matrix_UB_22      -0.1216643000
_diffrn_orient_matrix_UB_23      -0.0004385000
_diffrn_orient_matrix_UB_31      -0.1426921000
_diffrn_orient_matrix_UB_32      -0.0174640000
_diffrn_orient_matrix_UB_33      -0.0033826000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0440
_diffrn_reflns_av_unetI/netI     0.0302
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            46168
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.693
_diffrn_reflns_theta_min         2.379
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.785
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.451
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.54a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear pink'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.261
_exptl_crystal_description       plate
_exptl_crystal_F_000             1044
_exptl_crystal_size_max          0.499
_exptl_crystal_size_mid          0.312
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.445
_refine_diff_density_min         -0.475
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     675
_refine_ls_number_reflns         10686
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0483
_refine_ls_R_factor_gt           0.0420
_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^)+(0.0604P)^2^+0.9870P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1129
_refine_ls_wR_factor_ref         0.1182
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9327
_reflns_number_total             10686
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc05598c2.cif
_cod_data_source_block           compound2
_cod_depositor_comments
'Adding full bibliography for 1557449--1557455.cif.'
_cod_original_cell_volume        2578.25(13)
_cod_database_code               1557449
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C55H72ClF3N3O3PS
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.470
_diffrn_oxdiff_digest_frames
;
01b398728a16ea12b9fc2eda7727766f6d0314356fd
;
_diffrn_oxdiff_digest_hkl
;
0123ca9911f43a4794f9ebcb5eeb0c47a3ff5e
;
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     42.14
_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. Uiso/Uaniso restraints and constraints
Uanis(C55B) = Uanis(C55)
Uanis(C13) = Uanis(C13B)
3. Rigid body (RIGU) restrains
 F1, F1B, F2, F2B, F3, F3B, O1, O2, O3, C55, C55B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C13B)=Sof(H13B)=Sof(C14B)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C15B)=
 Sof(H15D)=Sof(H15E)=Sof(H15F)=1-FVAR(1)
 Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(H15A)=
 Sof(H15B)=Sof(H15C)=FVAR(1)
 Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(C55B)=1-FVAR(2)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(C55)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C10(H10), C13(H13), C13B(H13B), C22(H22), C25(H25), C49(H49), C52(H52)
5.b Secondary CH2 refined with riding coordinates:
 C37(H37A,H37B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C7(H7), C8(H8), C18(H18), C19(H19), C20(H20),
 C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C45(H45), C46(H46), C47(H47)
5.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C14B(H14D,H14E,
 H14F), C15(H15A,H15B,H15C), C15B(H15D,H15E,H15F), C23(H23A,H23B,H23C),
 C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C39(H39A,H39B,
 H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C50(H50A,
 H50B,H50C), C51(H51A,H51B,H51C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C)
;
_shelx_res_checksum              61266
_olex2_date_sample_data_collection 2019-06-28
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.878
_oxdiff_exptl_absorpt_empirical_full_min 0.376