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_1557455
_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(C57 H76 N3 P), C H2 Cl2, 2(Cl4 Ga)'
_chemical_formula_sum            'C115 H154 Cl10 Ga2 N6 P2'
_chemical_formula_weight         2176.31
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-07
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2018.12.18 svn.r3554 for Rigaku Oxford Diffraction, GUI svn.r1)
;
_audit_update_record
;
2019-08-28 deposited with the CCDC.	2020-01-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.3980(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   40.7612(6)
_cell_length_b                   12.3237(2)
_cell_length_c                   23.4798(3)
_cell_measurement_reflns_used    19995
_cell_measurement_temperature    100.00(13)
_cell_measurement_theta_max      30.0650
_cell_measurement_theta_min      1.7150
_cell_volume                     11562.0(3)
_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      100.00(13)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0951
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.939
_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      4.00  94.00   1.00   50.00    --   26.03  77.00 -60.00   90
  2  \w      6.00  81.00   1.00   50.00    --   26.03  57.00  60.00   75
  3  \w    -20.00  68.00   1.00   50.00    --   26.03 -99.00  30.00   88
  4  \w     65.00  92.00   1.00   50.00    --   26.03  57.00 -90.00   27
  5  \w     -4.00  40.00   1.00   50.00    --   26.03  77.00 120.00   44
  6  \w    -46.00  43.00   1.00   50.00    --   26.03 -38.00 150.00   89
  7  \w     -3.00  96.00   1.00   50.00    --   26.03  77.00-150.00   99
  8  \w    -20.00  64.00   1.00   50.00    --   26.03 -99.00 120.00   84
  9  \w      6.00  98.00   1.00   50.00    --   26.03  38.00-180.00   92
 10  \w     31.00  68.00   1.00   50.00    --   26.03 -99.00-120.00   37
 11  \w    -46.00  50.00   1.00   50.00    --   26.03 -38.00-120.00   96
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0106635000
_diffrn_orient_matrix_UB_12      0.0338969000
_diffrn_orient_matrix_UB_13      -0.0126739000
_diffrn_orient_matrix_UB_21      0.0132270000
_diffrn_orient_matrix_UB_22      -0.0096027000
_diffrn_orient_matrix_UB_23      0.0240404000
_diffrn_orient_matrix_UB_31      0.0051517000
_diffrn_orient_matrix_UB_32      -0.0455260000
_diffrn_orient_matrix_UB_33      -0.0145084000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0542
_diffrn_reflns_av_unetI/netI     0.0444
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.939
_diffrn_reflns_limit_h_max       60
_diffrn_reflns_limit_h_min       -59
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            114564
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.939
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.141
_diffrn_reflns_theta_min         1.729
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.773
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.788
_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            'metallic blue'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.250
_exptl_crystal_description       irregular
_exptl_crystal_F_000             4592
_exptl_crystal_size_max          0.243
_exptl_crystal_size_mid          0.125
_exptl_crystal_size_min          0.026
_refine_diff_density_max         0.897
_refine_diff_density_min         -0.567
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     770
_refine_ls_number_reflns         19086
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0873
_refine_ls_R_factor_gt           0.0517
_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^)+(0.0337P)^2^+16.7374P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1046
_refine_ls_wR_factor_ref         0.1194
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13305
_reflns_number_total             19086
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc05598c2.cif
_cod_data_source_block           compound7
_cod_depositor_comments
'Adding full bibliography for 1557449--1557455.cif.'
_cod_database_code               1557455
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C60 H83 Cl4 Ga N3 P'
_diffrn_oxdiff_digest_frames
;
019ce2a469788d27ea216cb61690ebaa25008590398
;
_diffrn_oxdiff_digest_hkl
;
01d24ad9bc4e9761f5017a8e86266a2763205b
;
_reflns_odcompleteness_completeness 99.98
_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. Uiso/Uaniso restraints and constraints
Uanis(C44) = Uanis(C44B)
Uanis(C43) = Uanis(C43B)
Uanis(C42) = Uanis(C42B)
Uanis(C41) = Uanis(C41B)
3. Others
 Sof(C39B)=Sof(C40B)=Sof(C41B)=Sof(H41B)=Sof(C42B)=Sof(H42B)=Sof(C43B)=
 Sof(H43B)=Sof(C44B)=Sof(C45B)=Sof(H45B)=Sof(C46B)=Sof(H46D)=Sof(H46E)=
 Sof(H46F)=Sof(C47B)=Sof(H47D)=Sof(H47E)=Sof(H47F)=Sof(C48B)=Sof(H48B)=
 Sof(C49B)=Sof(H49D)=Sof(H49E)=Sof(H49F)=Sof(C50B)=Sof(H50D)=Sof(H50E)=
 Sof(H50F)=1-FVAR(1)
 Sof(C39)=Sof(C40)=Sof(C41)=Sof(H41)=Sof(C42)=Sof(H42)=Sof(C43)=Sof(H43)=
 Sof(C44)=Sof(C45)=Sof(H45)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(C47)=
 Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(C48)=Sof(H48)=Sof(C49)=Sof(H49A)=Sof(H49B)=
 Sof(H49C)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=FVAR(1)
 Fixed Sof: Cl9(0.5) Cl10(0.5) C58(0.5) H58A(0.5) H58B(0.5) Ga1(0.5) Cl1(0.5)
 Cl2(0.5) Cl3(0.5) Cl4(0.5) Ga2(0.5) Cl5(0.5) Cl6(0.5) Cl7(0.5) Cl8(0.5)
4.a Ternary CH refined with riding coordinates:
 C10(H10), C13(H13), C22(H22), C25(H25), C45(H45), C48(H48), C45B(H45B),
 C48B(H48B)
4.b Secondary CH2 refined with riding coordinates:
 C37(H37A,H37B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,
 H56B), C57(H57A,H57B), C58(H58A,H58B)
4.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), C41(H41), C42(H42), C43(H43),
  C41B(H41B), C42B(H42B), C43B(H43B)
4.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), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C46(H46A,H46B,H46C),
 C47(H47A,H47B,H47C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C46B(H46D,H46E,
 H46F), C47B(H47D,H47E,H47F), C49B(H49D,H49E,H49F), C50B(H50D,H50E,H50F)
;
_shelx_res_checksum              623
_olex2_date_sample_data_collection 2019-06-05
_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 1.312
_oxdiff_exptl_absorpt_empirical_full_min 0.825