Isolation of Elusive Electrophilic Phosphinidene Complexes with π-Donor N-Heterocyclic Vinyl Substituents.
Rottschäfer, Dennis; Neumann, Beate; Stammler, Hans-Georg; Andrada, Diego Marcelo; Ghadwal, Rajendra S.; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c00176

data_4038310
_publ_section_title
;
 Isolation of Elusive Electrophilic Phosphinidene Complexes with \p-Donor
 N-Heterocyclic Vinyl Substituents.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c00176
_journal_year                    2020
_chemical_formula_moiety         'C45 H53 Fe N4 O4 P'
_chemical_formula_sum            'C45 H53 Fe N4 O4 P'
_chemical_formula_weight         800.73
_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             2019-08-20
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_cell_angle_alpha                90
_cell_angle_beta                 103.111(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.3827(2)
_cell_length_b                   20.2897(4)
_cell_length_c                   20.0193(4)
_cell_measurement_reflns_used    32454
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      32.5690
_cell_measurement_theta_min      2.6600
_cell_volume                     4107.37(14)
_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 0.998
_diffrn_measured_fraction_theta_max 0.943
_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    -32.00  10.00   1.00   12.00    --  -17.08 -77.00  60.00   42
  2  \w    -39.00  25.00   1.00   12.00    --   17.08 -19.00-180.00   64
  3  \w      1.00  86.00   1.00   12.00    --   17.08  38.00 150.00   85
  4  \w    -50.00  42.00   1.00   12.00    --   17.08 -57.00  30.00   92
  5  \w      6.00  80.00   1.00   12.00    --   17.08  57.00  30.00   74
  6  \w     24.00  80.00   1.00   12.00    --   17.08  38.00-150.00   56
  7  \w     -7.00  85.00   1.00   12.00    --   17.08  57.00 -60.00   92
  8  \w    -41.00  47.00   1.00   12.00    --   17.08 -77.00 150.00   88
  9  \w     39.00  91.00   1.00   12.00    --   17.08-154.00-119.58   52
 10  \w      3.00  69.00   1.00   12.00    --   17.08-121.00 -18.63   66
;
_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      -0.0430025000
_diffrn_orient_matrix_UB_12      0.0262774000
_diffrn_orient_matrix_UB_13      0.0035236000
_diffrn_orient_matrix_UB_21      -0.0518806000
_diffrn_orient_matrix_UB_22      -0.0228756000
_diffrn_orient_matrix_UB_23      -0.0004905000
_diffrn_orient_matrix_UB_31      0.0194709000
_diffrn_orient_matrix_UB_32      -0.0028714000
_diffrn_orient_matrix_UB_33      0.0362070000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0376
_diffrn_reflns_av_unetI/netI     0.0292
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.943
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            93700
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.943
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.799
_diffrn_reflns_theta_min         2.667
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.454
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.335
_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 dark orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.295
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1696
_exptl_crystal_size_max          0.335
_exptl_crystal_size_mid          0.272
_exptl_crystal_size_min          0.231
_refine_diff_density_max         0.673
_refine_diff_density_min         -0.500
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     508
_refine_ls_number_reflns         14364
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0535
_refine_ls_R_factor_gt           0.0411
_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^)+(0.0506P)^2^+2.4919P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1048
_refine_ls_wR_factor_ref         0.1120
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11939
_reflns_number_total             14364
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00176_si_004.cif
_cod_data_source_block           compound5
_cod_original_cell_volume        4107.35(14)
_cod_database_code               4038310
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C45H53FeN4O4P
_diffrn_oxdiff_digest_frames
;
0127ad2db6675198d5f14ed57ab2ac5c9c007156ae3
;
_diffrn_oxdiff_digest_hkl
;
01ba77e56d64ff4c3e2b436c1cff0d94c0e2ab
;
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     29.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C14(H14), C17(H17), C26(H26), C29(H29)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C10(H10), C11(H11), C12(H12), C22(H22), C23(H23), C24(H24),
 C33(H33), C34(H34), C35(H35), C36(H36), C37(H37)
2.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C31(H31A,
 H31B,H31C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C),
 C41(H41A,H41B,H41C)
;
_shelx_res_checksum              71669
_shelx_hkl_checksum              37002
_olex2_date_sample_data_collection 2019-08-20
_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 1.106
_oxdiff_exptl_absorpt_empirical_full_min 0.940