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_1557452
_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         '2(Cl4 Ga1), C54 H72 N3 P'
_chemical_formula_sum            'C54 H72 Cl8 Ga2 N3 P'
_chemical_formula_weight         1217.15
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   24.13916(17)
_cell_length_b                   18.90210(13)
_cell_length_c                   26.08922(18)
_cell_measurement_reflns_used    108311
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.4020
_cell_measurement_theta_min      2.9260
_cell_volume                     11904.01(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 0.994
_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    -59.00  33.00   1.00    4.50    --  -38.50  38.00  30.00   92
  2  \w    -92.00  -2.00   1.00    4.50    --  -38.50 125.00  30.00   90
  3  \w   -116.00  -5.00   1.00    4.50    --  -38.50 -19.00-150.00  111
  4  \w    -59.00  33.00   1.00    4.50    --  -38.50  38.00 -60.00   92
  5  \w    -64.00  30.00   1.00    4.50    --  -38.50  57.00-150.00   94
  6  \w     13.00 114.00   1.00    4.50    --   42.89  77.00 -90.00  101
  7  \w     18.00 111.00   1.00    4.50    --   42.89  57.00  60.00   93
  8  \w     13.00 114.00   1.00    4.50    --   42.89  77.00  90.00  101
  9  \w     22.00 114.00   1.00    4.50    --   42.89  38.00 -60.00   92
 10  \w     13.00 114.00   1.00    4.50    --   42.89  77.00-150.00  101
 11  \w     22.00 114.00   1.00    4.50    --   42.89  38.00  60.00   92
 12  \w     13.00 114.00   1.00    4.50    --   42.89  77.00 -30.00  101
 13  \w     13.00 114.00   1.00    4.50    --   42.89  77.00  30.00  101
 14  \w     13.00 114.00   1.00    4.50    --   42.89  77.00 150.00  101
 15  \w     23.00  97.00   1.00    4.50    --   42.89-125.00 -60.00   74
 16  \w     82.00 178.00   1.00   17.50    --  111.00  74.00   8.40   96
 17  \w     83.00 178.00   1.00   17.50    --  111.00  70.00 125.09   95
 18  \w     84.00 178.00   1.00   17.50    --  111.00  64.00 110.32   94
 19  \w     83.00 178.00   1.00   17.50    --  111.00  69.00  -2.26   95
 20  \w     41.00 118.00   1.00   17.50    --  111.00-125.00   0.00   77
 21  \w     84.00 178.00   1.00   17.50    --  111.00  65.00 146.61   94
 22  \w     81.00 178.00   1.00   17.50    --  111.00  77.00  30.00   97
 23  \w     85.00 178.00   1.00   17.50    --  111.00  61.00   0.00   93
 24  \w     81.00 178.00   1.00   17.50    --  111.00  77.00-120.00   97
 25  \w     41.00 118.00   1.00   17.50    --  111.00-125.00  60.00   77
 26  \w     31.00 110.00   1.00   17.50    --  111.00 -94.00  60.00   79
 27  \w     81.00 178.00   1.00   17.50    --  111.00  77.00 -30.00   97
 28  \w     83.00 178.00   1.00   17.50    --  111.00  67.00  91.75   95
 29  \w     87.00 178.00   1.00   17.50    --  111.00  51.00  78.52   91
 30  \w     40.00 141.00   1.00   17.50    --  111.00 -77.00  90.00  101
 31  \w     81.00 178.00   1.00   17.50    --  111.00  77.00  60.00   97
 32  \w     85.00 178.00   1.00   17.50    --  111.00  61.00-150.00   93
 33  \w     81.00 178.00   1.00   17.50    --  111.00  77.00 150.00   97
 34  \w     84.00 116.00   1.00   17.50    --  111.00  65.00 -59.94   32
;
_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      0.0240441000
_diffrn_orient_matrix_UB_12      -0.0183275000
_diffrn_orient_matrix_UB_13      0.0530738000
_diffrn_orient_matrix_UB_21      -0.0267311000
_diffrn_orient_matrix_UB_22      -0.0738777000
_diffrn_orient_matrix_UB_23      -0.0030308000
_diffrn_orient_matrix_UB_31      0.0527079000
_diffrn_orient_matrix_UB_32      -0.0291312000
_diffrn_orient_matrix_UB_33      -0.0257460000
_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  0.0607
_diffrn_reflns_av_unetI/netI     0.0161
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            220917
_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         76.871
_diffrn_reflns_theta_min         3.388
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.946
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.436
_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 light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.358
_exptl_crystal_description       irregular
_exptl_crystal_F_000             5040
_exptl_crystal_size_max          0.375
_exptl_crystal_size_mid          0.189
_exptl_crystal_size_min          0.167
_refine_diff_density_max         2.495
_refine_diff_density_min         -0.866
_refine_diff_density_rms         0.078
_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     669
_refine_ls_number_reflns         12495
_refine_ls_number_restraints     95
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0497
_refine_ls_R_factor_gt           0.0476
_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^)+(0.0616P)^2^+22.7445P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1232
_refine_ls_wR_factor_ref         0.1251
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11792
_reflns_number_total             12495
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc05598c2.cif
_cod_data_source_block           compound8
_cod_depositor_comments
'Adding full bibliography for 1557449--1557455.cif.'
_cod_original_cell_volume        11904.01(15)
_cod_database_code               1557452
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C54 H72 Cl8 Ga2 N3 P'
_diffrn_oxdiff_digest_frames
;
019273a6e4b4457d42a2e5b88a3944337b032597384
;
_diffrn_oxdiff_digest_hkl
;
010d96ab57956881693c726fcba756e7001dd8
;
_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. Restrained distances
 Ga1B-Cl1 \\sim Ga1A-Cl1 \\sim Ga1C-Cl1 \\sim Ga1B-Cl4B \\sim Ga1A-Cl4A \\sim
Ga1C-Cl4C \\sim Ga1C-
 Cl2C \\sim Ga1A-Cl2A \\sim Ga1B-Cl2B \\sim Ga1C-Cl3C \\sim Ga1A-Cl3A \\sim
Ga1B-Cl3B
 with sigma of 0.02
 Ga2B-Cl8B \\sim Ga2A-Cl8A \\sim Ga2A-Cl5 \\sim Ga2B-Cl5 \\sim Ga2B-Cl6B \\sim
Ga2A-Cl6A \\sim Ga2B-
 Cl7B \\sim Ga2A-Cl7A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Ga1C) = Uanis(Ga1A) = Uanis(Ga1B)
Uanis(Cl2C) = Uanis(Cl2A) = Uanis(Cl2B)
Uanis(Cl3C) = Uanis(Cl3A) = Uanis(Cl3B)
Uanis(Cl4A) = Uanis(Cl4C) = Uanis(Cl4B)
Uanis(Cl6B) = Uanis(Cl6A)
Uanis(Cl7A) = Uanis(Cl7B)
Uanis(Cl8B) = Uanis(Cl8A)
Uanis(Ga2A) = Uanis(Ga2B)
4. Others
 1*[Sof(Ga1A)+Sof(Cl2A)+Sof(Cl3A)+Sof(Cl4A)]+1*[Sof(Ga1B)+Sof(Cl2B)+Sof(Cl3B)+
 Sof(Cl4B)]+1*[Sof(Ga1C)+Sof(Cl2C)+Sof(Cl3C)+Sof(Cl4C)]=1 with esd of 0
 Sof(Ga1A)=Sof(Cl2A)=Sof(Cl3A)=Sof(Cl4A)=FVAR(1)
 Sof(Ga1B)=Sof(Cl2B)=Sof(Cl3B)=Sof(Cl4B)=FVAR(2)
 Sof(Ga1C)=Sof(Cl2C)=Sof(Cl3C)=Sof(Cl4C)=FVAR(3)
 Sof(Ga2B)=Sof(Cl6B)=Sof(Cl7B)=Sof(Cl8B)=1-FVAR(4)
 Sof(Ga2A)=Sof(Cl6A)=Sof(Cl7A)=Sof(Cl8A)=FVAR(4)
5.a Ternary CH refined with riding coordinates:
 C10(H10), C13(H13), 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), 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              53162
_olex2_date_sample_data_collection 2019-06-24
_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 2.643
_oxdiff_exptl_absorpt_empirical_full_min 0.444