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_1557453
_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, Cl4 Ga'
_chemical_formula_sum            'C54 H72 Cl4 Ga N3 P'
_chemical_formula_weight         1005.63
_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             2019-04-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-08-28 deposited with the CCDC.	2020-01-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.7240(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5123(2)
_cell_length_b                   12.8811(2)
_cell_length_c                   37.2397(5)
_cell_measurement_reflns_used    60415
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      32.7800
_cell_measurement_theta_min      3.0020
_cell_volume                     5472.21(15)
_computing_cell_refinement       'CrysAlisPro 1.171.40.47a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.47a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.47a (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 0.998
_diffrn_measured_fraction_theta_max 0.940
_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    -87.00  12.00   1.00   81.50    --  -17.14 -77.00 -90.00   99
  2  \w     17.00  91.00   1.00   81.50    --   17.14-154.00-127.09   74
  3  \w     -8.00  82.00   1.00   81.50    --   17.14  57.00-150.00   90
  4  \w     -4.00  83.00   1.00   81.50    --   17.14  38.00 120.00   87
  5  \w     -4.00  88.00   1.00   81.50    --   17.14  38.00  30.00   92
  6  \w    -53.00  28.00   1.00   81.50    --   17.14 -38.00 -60.00   81
  7  \w      6.00  75.00   1.00   81.50    --   17.14-131.00 -95.76   69
  8  \w    -47.00  47.00   1.00   81.50    --   17.14 -77.00  60.00   94
  9  \w     47.00  74.00   1.00   81.50    --   17.14-130.00  42.13   27
;
_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      -0.0151221000
_diffrn_orient_matrix_UB_12      -0.0199088000
_diffrn_orient_matrix_UB_13      0.0165089000
_diffrn_orient_matrix_UB_21      0.0553588000
_diffrn_orient_matrix_UB_22      -0.0248448000
_diffrn_orient_matrix_UB_23      0.0034246000
_diffrn_orient_matrix_UB_31      0.0239389000
_diffrn_orient_matrix_UB_32      0.0449363000
_diffrn_orient_matrix_UB_33      0.0092232000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0381
_diffrn_reflns_av_unetI/netI     0.0311
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.940
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       56
_diffrn_reflns_limit_l_min       -55
_diffrn_reflns_number            120621
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.940
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.788
_diffrn_reflns_theta_min         2.727
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.764
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.431
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.47a (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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.221
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2124
_exptl_crystal_size_max          0.411
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.231
_refine_diff_density_max         0.689
_refine_diff_density_min         -0.638
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.174
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     584
_refine_ls_number_reflns         19071
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.174
_refine_ls_R_factor_all          0.0642
_refine_ls_R_factor_gt           0.0544
_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^)+(0.0288P)^2^+4.9843P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1072
_refine_ls_wR_factor_ref         0.1106
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16638
_reflns_number_total             19071
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc05598c2.cif
_cod_data_source_block           compound6
_cod_depositor_comments
'Adding full bibliography for 1557449--1557455.cif.'
_cod_database_code               1557453
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C54 H92 Cl4 Ga N3 P'
_shelx_estimated_absorpt_t_max   0.843
_shelx_estimated_absorpt_t_min   0.744
_diffrn_oxdiff_digest_frames
;
017d6918fea4acc13ab1afa85533e8547500476707a
;
_diffrn_oxdiff_digest_hkl
;
015b83f5ac0d0b8e089321f4f3e997e0cac464
;
_reflns_odcompleteness_completeness 99.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.01
_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              65051
_olex2_date_sample_data_collection 2019-04-08
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.208
_oxdiff_exptl_absorpt_empirical_full_min 0.841