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_4038312
_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         'C36 H45 Cl2 N2 P, 1(C7 H8)'
_chemical_formula_sum            'C43 H53 Cl2 N2 P'
_chemical_formula_weight         699.74
_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             2019-01-25
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.3635(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.2047(2)
_cell_length_b                   16.3187(3)
_cell_length_c                   21.2446(4)
_cell_measurement_reflns_used    32699
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      30.2940
_cell_measurement_theta_min      3.1090
_cell_volume                     3884.41(12)
_computing_cell_refinement       'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.37a (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 0.999
_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    -86.00   8.00   1.00   35.00    --  -17.14 -57.00 -60.00   94
  2  \w    -13.00  88.00   1.00   35.00    --   17.14  77.00 -90.00  101
  3  \w     -4.00  88.00   1.00   35.00    --   17.14  38.00  60.00   92
  4  \w    -51.00  42.00   1.00   35.00    --   17.14 -57.00   0.00   93
  5  \w    -32.00  53.00   1.00   35.00    --   17.14 -90.00 126.75   85
  6  \w    -54.00  38.00   1.00   35.00    --   17.14 -38.00-120.00   92
  7  \w     -8.00  86.00   1.00   35.00    --   17.14  57.00 150.00   94
  8  \w      0.00  70.00   1.00   35.00    --   17.14-123.00 -32.40   70
  9  \w      0.00  70.00   1.00   35.00    --   17.14-123.00-150.03   70
 10  \w    -76.00 -27.00   1.00   35.00    --  -17.14 132.00 -51.63   49
 11  \w     -4.00  88.00   1.00   35.00    --   17.14  38.00 -90.00   92
;
_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      0.0103485000
_diffrn_orient_matrix_UB_12      -0.0333502000
_diffrn_orient_matrix_UB_13      0.0207233000
_diffrn_orient_matrix_UB_21      0.0466498000
_diffrn_orient_matrix_UB_22      0.0223004000
_diffrn_orient_matrix_UB_23      0.0148736000
_diffrn_orient_matrix_UB_31      -0.0415417000
_diffrn_orient_matrix_UB_32      0.0167019000
_diffrn_orient_matrix_UB_33      0.0215426000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0469
_diffrn_reflns_av_unetI/netI     0.0242
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            109374
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.034
_diffrn_reflns_theta_min         2.496
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.240
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.755
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.37a (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    1.197
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1496
_exptl_crystal_size_max          0.195
_exptl_crystal_size_mid          0.147
_exptl_crystal_size_min          0.126
_refine_diff_density_max         1.120
_refine_diff_density_min         -0.370
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     501
_refine_ls_number_reflns         11327
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0555
_refine_ls_R_factor_gt           0.0441
_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^)+(0.0511P)^2^+2.7161P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1130
_refine_ls_wR_factor_ref         0.1199
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9432
_reflns_number_total             11327
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00176_si_002.cif
_cod_data_source_block           compound2
_cod_original_cell_volume        3884.44(13)
_cod_database_code               4038312
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C36 H45 Cl2 N2 P'
_diffrn_oxdiff_digest_frames
;
017e4b5023e423361adf872a8b228215a2009523437
;
_diffrn_oxdiff_digest_hkl
;
01ead10dc2e73f92893dbfb2f0e6b8d22cd3be
;
_reflns_odcompleteness_completeness 99.57
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.01
_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. Uiso/Uaniso restraints and constraints
Uanis(C43B) = Uanis(C43)
3. Others
 Sof(C37B)=Sof(C38B)=Sof(H38B)=Sof(C39B)=Sof(H39B)=Sof(C40B)=Sof(H40B)=
 Sof(C41B)=Sof(H41B)=Sof(C42B)=Sof(H42B)=Sof(C43B)=Sof(H43D)=Sof(H43E)=
 Sof(H43F)=1-FVAR(1)
 Sof(C37)=Sof(C38)=Sof(H38)=Sof(C39)=Sof(H39)=Sof(C40)=Sof(H40)=Sof(C41)=
 Sof(H41)=Sof(C42)=Sof(H42)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C24(H24), C27(H27)
4.b Me refined with riding coordinates:
 C43(H43A,H43B,H43C), C43B(H43D,H43E,H43F)
4.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C20(H20), C21(H21), C22(H22), C32(H32), C33(H33),
 C34(H34), C35(H35), C36(H36), C38(H38), C39(H39), C40(H40), C41(H41), C42(H42),
  C38B(H38B), C39B(H39B), C40B(H40B), C41B(H41B), C42B(H42B)
4.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C)
;
_shelx_res_checksum              83525
_shelx_hkl_checksum              89198
_olex2_date_sample_data_collection 2019-01-24
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.111
_oxdiff_exptl_absorpt_empirical_full_min 0.916