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_1557450
_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         'Cl7 Ga2, Cl4 Ga, 2(C H2 Cl2), C57 H76 N3 P'
_chemical_formula_sum            'C59 H80 Cl15 Ga3 N3 P'
_chemical_formula_weight         1603.14
_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             2019-08-27
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2019-09-05 deposited with the CCDC.	2020-01-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.5840(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.16275(15)
_cell_length_b                   13.46701(10)
_cell_length_c                   28.2924(2)
_cell_measurement_reflns_used    76826
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      76.2540
_cell_measurement_theta_min      3.0950
_cell_volume                     7277.92(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.58a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.58a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.58a (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      100.0(1)
_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 0.995
_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    -64.00  30.00   1.00    2.50    --  -38.50  57.00-120.00   94
  2  \w    -59.00  33.00   1.00    2.50    --  -38.50  38.00  60.00   92
  3  \w     12.00  42.00   1.00    2.50    --   42.70  80.00  31.89   30
  4  \w     27.00  97.00   1.00    2.50    --   42.70-125.00  90.00   70
  5  \w     22.00 114.00   1.00    2.50    --   42.70  38.00 -90.00   92
  6  \w    -28.00  63.00   1.00    2.50    --   42.70 -38.00  60.00   91
  7  \w     22.00 114.00   1.00    2.50    --   42.70  38.00 120.00   92
  8  \w      6.00  81.00   1.00    2.50    --   42.70 -99.00 -60.00   75
  9  \w     11.00  42.00   1.00    2.50    --   42.70  81.00-144.67   31
 10  \w     12.00  42.00   1.00    2.50    --   42.70  78.00  69.28   30
 11  \w     16.00 111.00   1.00    2.50    --   42.70  63.00 147.36   95
 12  \w     12.00  42.00   1.00    2.50    --   42.70  80.00 -73.76   30
 13  \w     13.00  42.00   1.00    2.50    --   42.70  77.00-102.84   29
 14  \w     11.00  42.00   1.00    2.50    --   42.70  82.00 104.52   31
 15  \w     22.00 114.00   1.00    2.50    --   42.70  38.00 -30.00   92
 16  \w     18.00 111.00   1.00    2.50    --   42.70  57.00   0.00   93
 17  \w     12.00  42.00   1.00    2.50    --   42.70  79.00 -16.56   30
 18  \w     11.00  42.00   1.00    2.50    --   42.70  81.00 153.00   31
 19  \w     85.00 178.00   1.00   10.00    --  111.00  60.00-138.31   93
 20  \w     86.00 178.00   1.00   10.00    --  111.00  57.00 -98.41   92
 21  \w     85.00 156.00   1.00   10.00    --  111.00  61.00 -49.16   71
 22  \w     82.00 108.00   1.00   10.00    --  111.00  72.00  55.67   26
 23  \w     86.00 162.00   1.00   10.00    --  111.00  55.00  86.24   76
 24  \w     82.00 109.00   1.00   10.00    --  111.00  72.00 -85.23   27
 25  \w    146.00 173.00   1.00   10.00    --  111.00  72.00  55.67   27
 26  \w     82.00 176.00   1.00   10.00    --  111.00  72.00  36.97   94
 27  \w     85.00 112.00   1.00   10.00    --  111.00  61.00 -39.74   27
 28  \w     82.00 109.00   1.00   10.00    --  111.00  72.00 -30.57   27
 29  \w     83.00 109.00   1.00   10.00    --  111.00  68.00 -13.20   26
 30  \w     44.00 136.00   1.00   10.00    --  111.00 -61.00   0.00   92
 31  \w     86.00 159.00   1.00   10.00    --  111.00  61.00 -83.73   73
 32  \w     85.00 158.00   1.00   10.00    --  111.00  62.00 -66.44   73
 33  \w     87.00 114.00   1.00   10.00    --  111.00  53.00-152.47   27
 34  \w    144.00 177.00   1.00   10.00    --  111.00  57.00-122.94   33
 35  \w     86.00 112.00   1.00   10.00    --  111.00  57.00-122.94   26
 36  \w     88.00 170.00   1.00   10.00    --  111.00  47.00  30.60   82
 37  \w    120.00 176.00   1.00   10.00    --  111.00  58.00 137.18   56
 38  \w     86.00 112.00   1.00   10.00    --  111.00  58.00 137.18   26
 39  \w     87.00 178.00   1.00   10.00    --  111.00  50.00 154.95   91
 40  \w     83.00 176.00   1.00   10.00    --  111.00  67.00 170.59   93
 41  \w     31.00 107.00   1.00   10.00    --  111.00 -94.00-180.00   76
 42  \w     31.00 105.00   1.00   10.00    --  111.00 -94.00   0.00   74
 43  \w     83.00 109.00   1.00   10.00    --  111.00  69.00 -64.25   26
 44  \w     61.00 107.00   1.00   10.00    --  111.00-104.00 -34.71   46
 45  \w     81.00 108.00   1.00   10.00    --  111.00-103.00 -95.02   27
 46  \w    123.00 178.00   1.00   10.00    --  111.00  65.00   1.26   55
 47  \w     82.00 109.00   1.00   10.00    --  111.00  73.00  20.39   27
 48  \w     83.00 113.00   1.00   10.00    --  111.00  68.00 157.81   30
 49  \w     85.00 177.00   1.00   10.00    --  111.00  61.00-150.00   92
 50  \w     43.00 134.00   1.00   10.00    --  111.00 -61.00-180.00   91
 51  \w     85.00 111.00   1.00   10.00    --  111.00  61.00  90.00   26
 52  \w     84.00 110.00   1.00   10.00    --  111.00  64.00  24.00   26
 53  \w     85.00 112.00   1.00   10.00    --  111.00  61.00 -90.00   27
 54  \w     85.00 112.00   1.00   10.00    --  111.00  61.00  60.00   27
 55  \w     83.00 109.00   1.00   10.00    --  111.00-110.00  80.98   26
 56  \w     86.00 113.00   1.00   10.00    --  111.00  61.00-120.00   27
 57  \w    152.00 178.00   1.00   10.00    --  111.00  61.00-120.00   26
 58  \w     85.00 112.00   1.00   10.00    --  111.00  61.00 150.00   27
 59  \w     84.00 110.00   1.00   10.00    --  111.00  65.00   1.26   26
 60  \w     85.00 112.00   1.00   10.00    --  111.00  61.00 120.00   27
 61  \w     42.00 113.00   1.00   10.00    --  111.00-125.00-180.00   71
 62  \w     39.00  66.00   1.00   10.00    --  111.00-110.00  80.98   27
 63  \w     85.00 178.00   1.00   10.00    --  111.00  61.00 -30.00   93
 64  \w     82.00 177.00   1.00   10.00    --  111.00  74.00  90.37   95
 65  \w     85.00 111.00   1.00   10.00    --  111.00  60.00 117.47   26
 66  \w     86.00 112.00   1.00   10.00    --  111.00  55.00-162.16   26
;
_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      0.0669592000
_diffrn_orient_matrix_UB_12      0.0342859000
_diffrn_orient_matrix_UB_13      0.0292074000
_diffrn_orient_matrix_UB_21      0.0437088000
_diffrn_orient_matrix_UB_22      -0.0720993000
_diffrn_orient_matrix_UB_23      -0.0279082000
_diffrn_orient_matrix_UB_31      0.0103903000
_diffrn_orient_matrix_UB_32      0.0819262000
_diffrn_orient_matrix_UB_33      -0.0367911000
_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  0.0721
_diffrn_reflns_av_unetI/netI     0.0265
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            160048
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.755
_diffrn_reflns_theta_min         3.134
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.866
_exptl_absorpt_correction_T_max  0.716
_exptl_absorpt_correction_T_min  0.169
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.58a (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    1.463
_exptl_crystal_description       irregular
_exptl_crystal_F_000             3272
_exptl_crystal_size_max          0.423
_exptl_crystal_size_mid          0.291
_exptl_crystal_size_min          0.205
_refine_diff_density_max         0.680
_refine_diff_density_min         -0.771
_refine_diff_density_rms         0.075
_refine_ls_extinction_coef       0.000055(14)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     745
_refine_ls_number_reflns         15269
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0384
_refine_ls_R_factor_gt           0.0360
_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^)+(0.0529P)^2^+7.1390P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0954
_refine_ls_wR_factor_ref         0.0974
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14273
_reflns_number_total             15269
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc05598c2.cif
_cod_data_source_block           compound9
_cod_depositor_comments
'Adding full bibliography for 1557449--1557455.cif.'
_cod_original_cell_volume        7277.92(10)
_cod_database_code               1557450
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C236 H320 Cl60 Ga12 N12 P4 '
_diffrn_oxdiff_digest_frames
;
01daf365e99f952ddea88f8f2f0b0a13620353757c2
;
_diffrn_oxdiff_digest_hkl
;
01b4283c6e2c41b5797aef955c991bd4411373
;
_reflns_odcompleteness_completeness 99.98
_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:
 C20(H20), C23(H23), C32(H32), C35(H35), C50(H50), C53(H53)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B),
 C13(H13A,H13B), C58(H58A,H58B), C59(H59A,H59B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C16(H16), C17(H17), C18(H18), C28(H28), C29(H29), C30(H30),
 C39(H39), C40(H40), C41(H41), C42(H42), C43(H43), C46(H46), C47(H47), C48(H48)
2.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C36(H36A,H36B,H36C), C37(H37A,
 H37B,H37C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C54(H54A,H54B,H54C),
 C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C)
;
_shelx_res_checksum              65402
_olex2_date_sample_data_collection 2019-08-26
_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 2.332
_oxdiff_exptl_absorpt_empirical_full_min 0.377