Expanding Ligand Space: Preparation, Characterization, and Synthetic Applications of Air-Stable, Odorless Di-tert-alkylphosphine Surrogates
Barber, Thomas; Argent, Stephen P.; Ball, Liam T.; ACS Catalysis  (2020) 5454–5461; doi:10.1021/acscatal.0c01414

data_4517613
_publ_section_title
;
 Expanding Ligand Space: Preparation, Characterization, and Synthetic
 Applications of Air-Stable, Odorless Di-tert-alkylphosphine Surrogates
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              5454
_journal_page_last               5461
_journal_paper_doi               10.1021/acscatal.0c01414
_journal_year                    2020
_chemical_formula_moiety         'C39 H34 P, C F3 O3 S, 0.9(C H2 Cl2)'
_chemical_formula_sum            'C40.9 H35.8 Cl1.8 F3 O3 P S'
_chemical_formula_weight         759.13
_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   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-07-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.9070(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5515(2)
_cell_length_b                   18.5889(2)
_cell_length_c                   17.7571(2)
_cell_measurement_reflns_used    29085
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      73.3080
_cell_measurement_theta_min      4.7570
_cell_volume                     3756.12(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.45a (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    'XT (Sheldrick, 2015)'
_diffrn_ambient_environment      'N2 gas'
_diffrn_ambient_temperature      120(2)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 5.2349
_diffrn_detector_type            'Agilent Diffraction Atlas S2 detector'
_diffrn_measured_fraction_theta_full 0.999
_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      7.00  39.00   1.00    5.00    --  -41.45  19.00-120.00   32
  2  \w     -4.00  21.00   1.00    5.00    --  -41.45  19.00  60.00   25
  3  \w   -121.00  -5.00   1.00    5.00    --  -41.45 -19.00  60.00  116
  4  \w     -3.00  34.00   1.00    5.00    --  -41.45  19.00  30.00   37
  5  \w    -10.00  32.00   1.00    5.00    --  -41.45  38.00-150.00   42
  6  \w     12.00  40.00   1.00    5.00    --   41.45  79.00   1.18   28
  7  \w      6.00  60.00   1.00    5.00    --   41.45 -99.00 -30.00   54
  8  \w      7.00  34.00   1.00    5.00    --   41.45  83.00  38.68   27
  9  \w     10.00  37.00   1.00    5.00    --   41.45  76.00  70.86   27
 10  \w      6.00  31.00   1.00    5.00    --   41.45  85.00 105.13   25
 11  \w     83.00 131.00   1.00   20.00    --  105.50  30.00 -90.00   48
 12  \w     67.00 101.00   1.00   20.00    --  105.50-125.00 120.00   34
 13  \w     82.00 113.00   1.00   20.00    --  105.50-125.00-120.00   31
 14  \w     62.00 113.00   1.00   20.00    --  105.50-125.00 -90.00   51
 15  \w     30.00  55.00   1.00   20.00    --  105.50 -30.00-120.00   25
 16  \w     29.00  56.00   1.00   20.00    --  105.50 -30.00 -90.00   27
 17  \w     81.00 107.00   1.00   20.00    --  105.50-102.00  52.56   26
 18  \w     82.00 113.00   1.00   20.00    --  105.50-125.00  30.00   31
 19  \w     33.00  68.00   1.00   20.00    --  105.50-125.00  30.00   35
 20  \w     32.00  57.00   1.00   20.00    --  105.50 -45.00  30.00   25
 21  \w    103.00 155.00   1.00   20.00    --  105.50 125.00 -90.00   52
 22  \w     57.00  84.00   1.00   20.00    --  105.50 -61.00 120.00   27
 23  \w     58.00 112.00   1.00   20.00    --  105.50-125.00-180.00   54
 24  \w     30.00  55.00   1.00   20.00    --  105.50 -30.00   0.00   25
 25  \w     41.00  86.00   1.00   20.00    --  105.50 -77.00  90.00   45
 26  \w     34.00  92.00   1.00   20.00    --  105.50 -61.00-120.00   58
 27  \w     81.00 110.00   1.00   20.00    --  105.50-125.00 -30.00   29
 28  \w     98.00 147.00   1.00   20.00    --  105.50 125.00   0.00   49
 29  \w     37.00  64.00   1.00   20.00    --  105.50 -94.00   0.00   27
 30  \w     75.00 106.00   1.00   20.00    --  105.50 -94.00   0.00   31
 31  \w     29.00  56.00   1.00   20.00    --  105.50 -30.00 120.00   27
 32  \w     29.00 107.00   1.00   20.00    --  105.50 -77.00 106.50   78
 33  \w     81.00 114.00   1.00   20.00    --  105.50 -77.00 -30.00   33
 34  \w     34.00  78.00   1.00   20.00    --  105.50 -77.00 -30.00   44
 35  \w     58.00  89.00   1.00   20.00    --  105.50 -61.00  30.00   31
 36  \w     77.00 104.00   1.00   20.00    --  105.50 -94.00 -60.00   27
 37  \w    109.00 136.00   1.00   20.00    --  105.50  45.00-150.00   27
 38  \w     73.00 100.00   1.00   20.00    --  105.50 -94.00-120.00   27
 39  \w    119.00 146.00   1.00   20.00    --  105.50 125.00-120.00   27
 40  \w     97.00 123.00   1.00   20.00    --  105.50 125.00  60.00   26
 41  \w    127.00 154.00   1.00   20.00    --  105.50 125.00  60.00   27
 42  \w     35.00  90.00   1.00   20.00    --  105.50 -61.00 150.00   55
 43  \w     88.00 178.00   1.00   20.00    --  105.50  53.00 -93.94   90
 44  \w    125.00 161.00   1.00   20.00    --  105.50  77.00-150.00   36
 45  \w     81.00 165.00   1.00   20.00    --  105.50  45.00-180.00   84
 46  \w    121.00 170.00   1.00   20.00    --  105.50 125.00  30.00   49
 47  \w    122.00 167.00   1.00   20.00    --  105.50  61.00-120.00   45
 48  \w     86.00 113.00   1.00   20.00    --  105.50-125.00 -60.00   27
 49  \w     81.00 112.00   1.00   20.00    --  105.50-125.00 150.00   31
 50  \w     45.00  72.00   1.00   20.00    --  105.50 -61.00 -30.00   27
 51  \w     33.00  67.00   1.00   20.00    --  105.50-125.00  90.00   34
 52  \w     78.00 132.00   1.00   20.00    --  105.50  60.00 -36.34   54
 53  \w    146.00 171.00   1.00   20.00    --  105.50  60.00 -36.34   25
 54  \w    133.00 160.00   1.00   20.00    --  105.50  77.00 150.00   27
 55  \w     80.00 114.00   1.00   20.00    --  105.50  61.00-120.00   34
 56  \w     41.00  87.00   1.00   20.00    --  105.50 -94.00 -30.00   46
 57  \w     66.00  92.00   1.00   20.00    --  105.50 -61.00   0.00   26
 58  \w    130.00 178.00   1.00   20.00    --  105.50  77.00 -30.00   48
 59  \w     50.00  77.00   1.00   20.00    --  105.50-105.00 -51.00   27
 60  \w     81.00 108.00   1.00   20.00    --  105.50-105.00 -51.00   27
 61  \w    118.00 151.00   1.00   20.00    --  105.50 125.00 120.00   33
 62  \w    123.00 167.00   1.00   20.00    --  105.50 125.00 150.00   44
 63  \w     81.00 156.00   1.00   20.00    --  105.50  45.00 150.00   75
 64  \w    129.00 156.00   1.00   20.00    --  105.50 104.00 166.17   27
 65  \w    132.00 166.00   1.00   20.00    --  105.50  45.00 -60.00   34
 66  \w     47.00  75.00   1.00   20.00    --  105.50 -77.00  60.00   28
 67  \w     74.00 107.00   1.00   20.00    --  105.50-101.00 107.81   33
 68  \w     85.00 112.00   1.00   20.00    --  105.50  30.00-150.00   27
 69  \w     31.00  64.00   1.00   20.00    --  105.50-101.00 107.81   33
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Atlas S2'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0057931000
_diffrn_orient_matrix_UB_12      0.0800778000
_diffrn_orient_matrix_UB_13      0.0227811000
_diffrn_orient_matrix_UB_21      -0.1308370000
_diffrn_orient_matrix_UB_22      -0.0020226000
_diffrn_orient_matrix_UB_23      0.0075606000
_diffrn_orient_matrix_UB_31      0.0342410000
_diffrn_orient_matrix_UB_32      -0.0213586000
_diffrn_orient_matrix_UB_33      0.0847082000
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_wavelength_determination fundamental
_diffrn_reflns_av_R_equivalents  0.0651
_diffrn_reflns_av_unetI/netI     0.0278
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            61659
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.753
_diffrn_reflns_theta_min         3.885
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_target            Cu
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    2.789
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.272
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.45a (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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.342
_exptl_crystal_description       plate
_exptl_crystal_F_000             1575
_exptl_crystal_size_max          0.574
_exptl_crystal_size_mid          0.213
_exptl_crystal_size_min          0.052
_refine_diff_density_max         1.097
_refine_diff_density_min         -0.629
_refine_diff_density_rms         0.073
_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     555
_refine_ls_number_reflns         7546
_refine_ls_number_restraints     496
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0726
_refine_ls_R_factor_gt           0.0701
_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^)+(0.0893P)^2^+6.2759P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1794
_refine_ls_wR_factor_ref         0.1818
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7090
_reflns_number_total             7546
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01414_si_003.cif
_cod_data_source_block           tbltbn
_cod_depositor_comments
'Adding full bibliography for 4517604--4517617.cif.'
_cod_original_formula_sum        'C40.90 H35.80 Cl1.80 F3 O3 P S'
_cod_database_code               4517613
_nottingham_internal_coll_name   TBLTBN
_nottingham_internal_coll_number 18248
_nottingham_internal_coll_client TB/LTB
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '20.00, 5.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczspa
_nottingham_internal_coll_date   05/07/2019
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVB, PL13110001'
_nottingham_internal_process_date 08/07/2019
_nottingham_internal_process_user pczspa
_nottingham_internal_solution_date 27/07/2019
_nottingham_internal_solution_user pczspa
_nottingham_internal_refinement_date 27/07/2019
_nottingham_internal_refinement_user pczspa
_nottingham_internal_validation_date 27/07/2019
_nottingham_internal_validation_user pczspa
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C40H34F3O3PS
_chemical_oxdiff_usercomment
'GVB-1644 TBLTBN #18248 TB/LTB fomblin micromount'
_shelx_estimated_absorpt_t_max   0.869
_shelx_estimated_absorpt_t_min   0.297
_reflns_odcompleteness_completeness 98.20
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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 P(H) groups
2. Restrained distances
 S1A-C5A \\sim S1A-C5B
 with sigma of 0.02
 C71-C4 \\sim C61-C4
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C5A \\sim F6A \\sim F7A \\sim F8A \\sim C5B \\sim F8B \\sim F7B \\sim F6B:
within 2A with sigma of 0.008 and sigma for terminal atoms of 0.016
C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim C71 \\sim C72 \\sim
C73 \\sim C74 \\sim C75 \\sim C76: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
Uanis(C71) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C5A, F6A, F7A, F8A, C5B, F6B, F7B, F8B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C61, C62, C63, C64, C65, C66, C71, C72, C73, C74, C75, C76, C4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C61, C66, C65, C64, C63, C62} sigma for 1-2: 0.02, 1-3: 0.04
as
{C61, C62, C63, C64, C65, C66}
{C61, C62, C63, C64, C65, C66} sigma for 1-2: 0.02, 1-3: 0.04
{C61, C66, C65, C64, C63, C62} sigma for 1-2: 0.02, 1-3: 0.04
as
{C71, C72, C73, C74, C75, C76}
{C5A, F6A, F8A, F7A} sigma for 1-2: 0.02, 1-3: 0.04
{C5A, F7A, F8A, F6A} sigma for 1-2: 0.02, 1-3: 0.04
{C5A, F8A, F7A, F6A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C5A, F6A, F7A, F8A}
{C5A, F6A, F7A, F8A} sigma for 1-2: 0.02, 1-3: 0.04
{C5A, F6A, F8A, F7A} sigma for 1-2: 0.02, 1-3: 0.04
{C5A, F7A, F8A, F6A} sigma for 1-2: 0.02, 1-3: 0.04
{C5A, F8A, F7A, F6A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C5B, F6B, F7B, F8B}
6. Others
 Sof(H4B)=Sof(C71)=Sof(C72)=Sof(H72)=Sof(C73)=Sof(H73)=Sof(C74)=Sof(H74)=
 Sof(C75)=Sof(H75)=Sof(C76)=Sof(H76)=1-FVAR(1)
 Sof(H4A)=Sof(C61)=Sof(C62)=Sof(H62)=Sof(C63)=Sof(H63)=Sof(C64)=Sof(H64)=
 Sof(C65)=Sof(H65)=Sof(C66)=Sof(H66)=FVAR(1)
 Sof(C5B)=Sof(F6B)=Sof(F7B)=Sof(F8B)=1-FVAR(2)
 Sof(C5A)=Sof(F6A)=Sof(F7A)=Sof(F8A)=FVAR(2)
 Fixed Sof: C1B(0.9) H1BA(0.9) H1BB(0.9) Cl2B(0.9) Cl3B(0.9)
7.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C4(H4A), C4(H4B)
7.b Secondary CH2 refined with riding coordinates:
 C1B(H1BA,H1BB)
7.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C22(H22), C23(H23),
 C24(H24), C25(H25), C26(H26), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36),
  C42(H42), C43(H43), C44(H44), C45(H45), C46(H46), C52(H52), C53(H53),
 C54(H54), C55(H55), C56(H56), C62(H62), C63(H63), C64(H64), C65(H65), C66(H66),
  C72(H72), C73(H73), C74(H74), C75(H75), C76(H76)
;
_shelx_res_checksum              42973
_shelx_hkl_checksum              48306
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_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 1.674
_oxdiff_exptl_absorpt_empirical_full_min 0.587