Synthesis and reactivity of a parent phosphathioethynolato-borane and a boraarsaketene
Jürgensen, Malte; Kunz, Tanja; Arrowsmith, Merle; Dietz, Maximilian; Hagspiel, Stephan; Braunschweig, Holger; Chemical Science 16 (2025) 8870–8877; doi:10.1039/D5SC01996F

data_1574414
_publ_section_title
;
 Synthesis and reactivity of a parent phosphathioethynolato-borane and a
 boraarsaketene
;
_journal_issue                   20
_journal_name_full               'Chemical Science'
_journal_page_first              8870
_journal_page_last               8877
_journal_paper_doi               10.1039/D5SC01996F
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C56 H53 B2 N2 P S, C7 H8'
_chemical_formula_sum            'C63 H61 B2 N2 P S'
_chemical_formula_weight         930.78
_chemical_name_common            (SIMes)BH2C(Ph)B(Ph)S(C4PPh3)
_chemical_name_systematic        5
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-11-08
_audit_creation_method           'CIF-fill 1.3n (K.Radacki, 2005-22)'
_audit_update_record
;
2025-03-03 deposited with the CCDC.	2025-04-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.44370(10)
_cell_length_b                   20.19870(10)
_cell_length_c                   26.63090(10)
_cell_measurement_reflns_used    66366
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      74.7730
_cell_measurement_theta_min      2.7330
_cell_volume                     5079.86(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.68a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.68a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.68a (Rigaku OD, 2022)'
_computing_molecular_graphics    'ShelXLe (Huebschle et all, 2011)'
_computing_publication_material  'SHELXL-2019/2 (Sheldrick, 2019)'
_computing_structure_refinement  'SHELXL-2019/2 (Sheldrick, 2019)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 HPA
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'HyPix Arc150'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_details
;
 List of Runs (angles in degrees, time in seconds):
 --------------------------------------------------------------------------
  1  \w    101.00 127.40   0.60    0.50    --   85.25  41.00  88.93   44
  2  \w     98.00 131.00   0.60    0.50    --   85.25  55.00  41.41   55
  3  \w     71.00 104.60   0.60    0.50    --   58.00  52.00 -41.20   56
  4  \w     49.00 130.00   0.60    0.50    --   82.35  15.00 -90.00  135
  5  \w     99.00 131.40   0.60    0.50    --   85.25  48.00 -62.19   54
  6  \w     99.00 124.20   0.60    0.50    --   85.25  46.00 -27.99   42
  7  \w     96.00 135.00   0.60    0.50    --   85.25  35.00   9.19   65
  8  \w    108.00 134.40   0.60    0.50    --   85.25  35.00 159.86   44
  9  \w    103.00 130.60   0.60    0.50    --   85.25 134.00  78.09   46
 10  \w     98.00 131.00   0.60    0.50    --   85.25 128.00  53.67   55
 11  \w    102.00 129.60   0.60    0.50    --   85.25 119.00  31.28   46
 12  \w    101.00 131.00   0.60    0.50    --   85.25 125.00-109.11   50
 13  \w     46.00  87.40   0.60    0.50    --   85.25 -89.00  66.56   69
 14  \w     45.00  70.20   0.60    0.50    --   82.35-133.00  96.00   42
 15  \w     25.00  88.60   0.60    0.50    --   58.60-133.00  96.00  106
 16  \w     25.00  95.80   0.60    0.50    --   71.26-133.00  96.00  118
 17  \w     28.00  91.60   0.60    0.50    --   58.60-138.00 -79.00  106
 18  \w     43.00  68.20   0.60    0.50    --   71.26-138.00 -79.00   42
 19  \w     60.00  86.40   0.60    0.50    --   82.35-138.00 -79.00   44
 20  \w     42.00  92.40   0.60    0.50    --   85.25 -98.00-116.50   84
 21  \w     42.00  92.40   0.60    0.50    --   85.25-101.00-146.76   84
 22  \w     30.00  61.20   0.60    0.50    --   58.60-126.00 -90.00   52
 23  \w     61.00  92.20   0.60    0.50    --   85.25-105.00 -50.90   52
 24  \w     43.00  91.00   0.60    0.50    --   85.25 -96.00 -36.05   80
 25  \w     46.00  91.00   0.60    0.50    --   85.25 -96.00 -12.60   75
 26  \w     44.00  91.40   0.60    0.50    --   85.25 -96.00  14.48   79
 27  \w     42.00  93.00   0.60    0.50    --   85.25 -98.00 115.85   85
 28  \w     42.00  87.00   0.60    0.50    --   82.35 -95.00 150.00   75
 29  \w     45.00  90.00   0.60    0.50    --   85.25 -92.00  24.17   75
 30  \w     40.00  65.20   0.60    0.50    --   82.35 -95.00 -90.00   42
 31  \w     50.00  86.00   0.60    0.50    --   82.35 -95.00-180.00   60
 32  \w   -101.00 -75.80   0.60    0.50    --  -50.00 -40.00  61.18   42
 33  \w   -123.00 -91.80   0.60    0.50    --  -79.50 -62.00 120.43   52
 34  \w   -122.00 -95.60   0.60    0.50    --  -79.50 -63.00 179.42   44
 35  \w   -121.00 -88.60   0.60    0.50    --  -74.00 -56.00 131.67   54
 36  \w   -122.00 -96.80   0.60    0.50    --  -79.50 -65.00  21.10   42
 37  \w   -104.00 -77.00   0.60    0.50    --  -58.00 -52.00 -18.14   45
 38  \w   -117.00 -84.00   0.60    0.50    --  -70.00 -57.00 -89.72   55
 39  \w   -128.00 -98.60   0.60    0.50    --  -79.50 -49.00-121.65   49
 40  \w   -127.00-101.80   0.60    0.50    --  -79.50 -54.00-109.11   42
 41  \w   -104.00 -77.60   0.60    0.50    --  -62.00 -48.00   6.14   44
 42  \w   -129.00 -93.60   0.60    0.50    --  -79.50 -48.00  60.25   59
 43  \w   -125.00 -98.60   0.60    0.50    --  -79.50 -47.00  89.85   44
 44  \w   -115.00 -82.00   0.60    0.50    --  -66.00 -49.00 150.21   55
 45  \w    -98.00 -65.60   0.60    0.50    --  -50.00 -48.00 165.80   54
 46  \w   -122.00 -95.60   0.60    0.50    --  -79.50-140.00  67.65   44
 47  \w   -123.00 -91.80   0.60    0.50    --  -79.50-125.00  66.51   52
 48  \w   -126.00 -93.00   0.60    0.50    --  -79.50-123.00-150.99   55
 49  \w   -104.00 -23.00   0.60    0.50    --  -69.71 138.00 -18.00  135
 50  \w    -95.00 -23.00   0.60    0.50    --  -60.16 138.00 -18.00  120
 51  \w    -96.00 -42.60   0.60    0.50    --  -79.50 116.00-134.50   89
 52  \w    -93.00 -67.80   0.60    0.50    --  -76.30 138.00 -18.00   42
 53  \w    -97.00 -61.60   0.60    0.50    --  -78.00 114.00  21.95   59
 54  \w    -97.00 -34.00   0.60    0.50    --  -79.50 115.00  36.18  105
 55  \w    -63.00 -33.60   0.60    0.50    --  -78.00 114.00  11.16   49
 56  \w    -97.00 -64.60   0.60    0.50    --  -78.00 114.00  71.43   54
 57  \w    -97.00 -68.80   0.60    0.50    --  -78.00 114.00  11.16   47
 58  \w    -58.00 -32.80   0.60    0.50    --  -78.00 114.00  71.43   42
 59  \w    -92.00 -66.80   0.60    0.50    --  -79.50 102.00 124.80   42
 60  \w    -92.00 -66.80   0.60    0.50    --  -76.30 133.00 164.00   42
 61  \w   -101.00 -23.00   0.60    0.50    --  -69.71 133.00 164.00  130
 62  \w    -92.00 -20.00   0.60    0.50    --  -60.16 133.00 164.00  120
 63  \w    -92.00 -56.00   0.60    0.50    --  -79.50 102.00 150.51   60
 64  \w    -64.00 -38.80   0.60    0.50    --  -79.50 102.00 124.80   42
 65  \w    -87.00 -49.80   0.60    0.50    --  -79.50 103.00 -27.17   62
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB Synergy-R'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
;
 CrysAlisPro convention (1999,Acta A55,543-557)
;
_diffrn_orient_matrix_UB_11      -0.1234906000
_diffrn_orient_matrix_UB_12      0.0027455000
_diffrn_orient_matrix_UB_13      0.0377406000
_diffrn_orient_matrix_UB_21      -0.1065017000
_diffrn_orient_matrix_UB_22      0.0002684000
_diffrn_orient_matrix_UB_23      -0.0438415000
_diffrn_orient_matrix_UB_31      -0.0047541000
_diffrn_orient_matrix_UB_32      -0.0762001000
_diffrn_orient_matrix_UB_33      0.0011709000
_diffrn_radiation_monochromator  'multi-layer mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_xray_symbol    K-L~2,3~
_diffrn_reflns_av_R_equivalents  0.0237
_diffrn_reflns_av_unetI/netI     0.0111
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            103650
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.072
_diffrn_reflns_theta_min         2.746
_diffrn_source                   'rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet-R X-ray Source'
_exptl_absorpt_coefficient_mu    1.180
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.749
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
 CrysAlisPro 1.171.42.68a (Rigaku Oxford Diffraction, 2022) 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            yellow
_exptl_crystal_density_diffrn    1.217
_exptl_crystal_description       block
_exptl_crystal_F_000             1976
_exptl_crystal_preparation
;
 Crystalls were grown from saturated solution. For data collection the 
 crystal was immersed in a film of perfluoropolyether oil, mounted on a 
 polyimide loop and transferred to stream of cold nitrogen (Oxford Cryostream 
 800).
;
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.210
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.040
_refine_diff_density_max         0.311
_refine_diff_density_min         -0.314
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 4075 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, 
 Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.003(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     670
_refine_ls_number_reflns         9613
_refine_ls_number_restraints     312
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0297
_refine_ls_R_factor_gt           0.0291
_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^)+(0.0507P)^2^+1.2434P] where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0801
_refine_ls_wR_factor_ref         0.0805
_reflns_Friedel_coverage         0.796
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                9390
_reflns_number_total             9613
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01996f2.cif
_cod_data_source_block           MaDi265_MaJu_a
_cod_depositor_comments
'Adding full bibliography for 1574408--1574414.cif.'
_cod_database_code               1574414
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_min   0.790
_shelx_estimated_absorpt_t_max   0.954
_shelx_res_checksum              61190