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_1557454
_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 N3 P'
_chemical_formula_sum            'C54 H72 N3 P'
_chemical_formula_weight         794.11
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-26
_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                90
_cell_angle_beta                 93.5540(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.56270(10)
_cell_length_b                   15.9337(2)
_cell_length_c                   23.6169(2)
_cell_measurement_reflns_used    52810
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.3720
_cell_measurement_theta_min      3.2990
_cell_volume                     4718.31(8)
_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      100.00(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 0.994
_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    -85.00 -19.00   1.00    3.00    --  -38.50 -38.00  60.00   66
  2  \w    -51.00  33.00   1.00    3.00    --  -38.50  38.00  30.00   84
  3  \w   -107.00 -19.00   1.00    3.00    --  -38.50 -38.00-150.00   88
  4  \w    -69.00  29.00   1.00    3.00    --  -38.50  88.00-112.00   98
  5  \w    -47.00  30.00   1.00    3.00    --  -38.50  38.00-150.00   77
  6  \w     17.00  80.00   1.00    3.00    --   42.89  77.00 150.00   63
  7  \w      1.00  78.00   1.00    3.00    --   42.89 -99.00  90.00   77
  8  \w     13.00 114.00   1.00    3.00    --   42.89  77.00 -60.00  101
  9  \w     16.00  65.00   1.00    3.00    --   42.89  77.00-150.00   49
 10  \w     85.00 111.00   1.00    3.00    --   42.89  57.00 -90.00   26
 11  \w     16.00  60.00   1.00    3.00    --   42.89  77.00   0.00   44
 12  \w     18.00  64.00   1.00    3.00    --   42.89  57.00 -90.00   46
 13  \w     13.00  78.00   1.00    3.00    --   42.89  77.00  90.00   65
 14  \w     21.00  95.00   1.00    3.00    --   42.89  57.00  60.00   74
 15  \w     40.00  77.00   1.00   11.98    --  111.00 -77.00 -90.00   37
 16  \w     81.00 108.00   1.00   11.98    --  111.00  77.00 -60.00   27
 17  \w     81.00 107.00   1.00   11.98    --  111.00  76.00  86.29   26
 18  \w    113.00 175.00   1.00   11.98    --  111.00  77.00 -30.00   62
 19  \w     85.00 112.00   1.00   11.98    --  111.00  61.00 -60.00   27
 20  \w    119.00 153.00   1.00   11.98    --  111.00  51.00-160.62   34
 21  \w     84.00 111.00   1.00   11.98    --  111.00  64.00 -82.88   27
 22  \w     81.00 177.00   1.00   11.98    --  111.00  77.00  60.00   96
 23  \w     48.00 141.00   1.00   11.98    --  111.00 -77.00  60.00   93
 24  \w     81.00 107.00   1.00   11.98    --  111.00  77.00 -30.00   26
 25  \w     85.00 111.00   1.00   11.98    --  111.00  61.00   0.00   26
 26  \w     85.00 111.00   1.00   11.98    --  111.00  61.00  60.00   26
 27  \w     81.00 108.00   1.00   11.98    --  111.00  77.00-120.00   27
 28  \w     89.00 115.00   1.00   11.98    --  111.00  45.00  90.00   26
 29  \w     85.00 178.00   1.00   11.98    --  111.00  61.00 120.00   93
 30  \w     58.00 117.00   1.00   11.98    --  111.00-125.00  30.00   59
 31  \w     81.00 108.00   1.00   11.98    --  111.00  77.00 120.00   27
 32  \w     82.00 118.00   1.00   11.98    --  111.00-125.00 -60.00   36
 33  \w     86.00 177.00   1.00   11.98    --  111.00  61.00  30.00   91
 34  \w     83.00 178.00   1.00   11.98    --  111.00  68.00-144.88   95
 35  \w     87.00 115.00   1.00   11.98    --  111.00  51.00-160.62   28
 36  \w     85.00 111.00   1.00   11.98    --  111.00  61.00-120.00   26
 37  \w     81.00 176.00   1.00   11.98    --  111.00  77.00 150.00   95
 38  \w     41.00 118.00   1.00   11.98    --  111.00-125.00  90.00   77
 39  \w     85.00 111.00   1.00   11.98    --  111.00  61.00  90.00   26
 40  \w    116.00 178.00   1.00   11.98    --  111.00  77.00 -90.00   62
 41  \w     81.00 108.00   1.00   11.98    --  111.00  77.00   0.00   27
 42  \w    111.00 178.00   1.00   11.98    --  111.00  77.00   0.00   67
 43  \w     84.00 110.00   1.00   11.98    --  111.00  65.00-109.92   26
 44  \w     81.00 110.00   1.00   11.98    --  111.00  77.00  90.00   29
 45  \w    121.00 171.00   1.00   11.98    --  111.00  77.00  90.00   50
 46  \w     85.00 120.00   1.00   11.98    --  111.00  61.00 -30.00   35
 47  \w     81.00 107.00   1.00   11.98    --  111.00  77.00 -90.00   26
 48  \w     83.00 109.00   1.00   11.98    --  111.00  77.00  30.00   26
 49  \w     81.00 107.00   1.00   11.98    --  111.00  77.00-180.00   26
 50  \w     85.00 111.00   1.00   11.98    --  111.00  61.00-180.00   26
 51  \w     85.00 147.00   1.00   11.98    --  111.00  61.00-150.00   62
 52  \w     42.00  93.00   1.00   11.98    --  111.00 -77.00-150.00   51
 53  \w    107.00 141.00   1.00   11.98    --  111.00 -77.00-150.00   34
 54  \w     85.00 111.00   1.00   11.98    --  111.00  61.00 -90.00   26
 55  \w     85.00 125.00   1.00   11.98    --  111.00  61.00 150.00   40
 56  \w    109.00 178.00   1.00   11.98    --  111.00  77.00-120.00   69
 57  \w    114.00 139.00   1.00   11.98    --  111.00 -77.00 -90.00   25
 58  \w     82.00 108.00   1.00   11.98    --  111.00  72.00   0.65   26
 59  \w     85.00 177.00   1.00   11.98    --  111.00  59.00  46.28   92
 60  \w     63.00  64.00   1.00   11.98    --  111.00-125.00-150.00    1
;
_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      0.0035436000
_diffrn_orient_matrix_UB_12      -0.0427493000
_diffrn_orient_matrix_UB_13      -0.0583530000
_diffrn_orient_matrix_UB_21      -0.1218682000
_diffrn_orient_matrix_UB_22      0.0095195000
_diffrn_orient_matrix_UB_23      -0.0093074000
_diffrn_orient_matrix_UB_31      0.0151921000
_diffrn_orient_matrix_UB_32      0.0861936000
_diffrn_orient_matrix_UB_33      -0.0279417000
_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  0.0355
_diffrn_reflns_av_unetI/netI     0.0152
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            86959
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.717
_diffrn_reflns_theta_min         3.348
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.788
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.543
_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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.118
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1728
_exptl_crystal_size_max          0.449
_exptl_crystal_size_mid          0.312
_exptl_crystal_size_min          0.219
_refine_diff_density_max         0.267
_refine_diff_density_min         -0.275
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     539
_refine_ls_number_reflns         9876
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0373
_refine_ls_R_factor_gt           0.0358
_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^)+(0.0477P)^2^+1.7295P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0921
_refine_ls_wR_factor_ref         0.0933
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9416
_reflns_number_total             9876
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc05598c2.cif
_cod_data_source_block           compound4
_cod_depositor_comments
'Adding full bibliography for 1557449--1557455.cif.'
_cod_database_code               1557454
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C54 H72 N3 P'
_diffrn_oxdiff_digest_frames
;
0180a4d5b456edcbad7a27c7fc6e55b281000283ddf
;
_diffrn_oxdiff_digest_hkl
;
01c9c8e4428880672235094ca7806e94f101d2
;
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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.a Ternary CH refined with riding coordinates:
 C10(H10), C13(H13), C22(H22), C25(H25), C49(H49), C52(H52)
2.b Secondary CH2 refined with riding coordinates:
 C37(H37A,H37B)
2.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)
2.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C15(H15A,H15B,
 H15C), 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              20090
_olex2_date_sample_data_collection 2019-06-25
_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 2.523
_oxdiff_exptl_absorpt_empirical_full_min 0.471