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_4517609
_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         'C34 H39 P'
_chemical_formula_sum            'C34 H39 P'
_chemical_formula_weight         478.62
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-11-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                111.882(2)
_cell_angle_beta                 109.918(2)
_cell_angle_gamma                96.579(2)
_cell_formula_units_Z            2
_cell_length_a                   10.1139(2)
_cell_length_b                   12.6246(3)
_cell_length_c                   13.5249(3)
_cell_measurement_reflns_used    11897
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.2450
_cell_measurement_theta_min      4.7370
_cell_volume                     1447.74(7)
_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    'ShelXT (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 4.2207
_diffrn_detector_type            'Agilent Diffraction Titan S2 detector'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.975
_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  22.00   1.00    5.00    --   30.00  85.00  -2.75   26
  2  \w     -4.00  24.00   1.00    5.00    --   30.00  87.00-115.86   28
  3  \w      3.00  28.00   1.00    5.00    --   38.00  90.00 154.88   25
  4  \w   -113.00 -20.00   1.00    5.00    --  -42.25 -38.00 150.00   93
  5  \w    -20.00  74.00   1.00    5.00    --   42.25 -77.00 150.00   94
  6  \w     27.00  95.00   1.00    5.00    --   42.25-125.00  60.00   68
  7  \w     15.00  42.00   1.00    5.00    --   46.00  76.00  88.05   27
  8  \w     14.00  39.00   1.00    5.00    --   46.00  79.00 -86.87   25
  9  \w     15.00  42.00   1.00    5.00    --   46.00  76.00 116.29   27
 10  \w     14.00  39.00   1.00    5.00    --   46.00  79.00  20.67   25
 11  \w     74.00 130.00   1.00    5.00    --   58.00  74.00-173.80   56
 12  \w     27.00  71.00   1.00    5.00    --   58.00  74.00 102.88   44
 13  \w     27.00  69.00   1.00    5.00    --   58.00  74.00 -86.98   42
 14  \w     81.00 112.00   1.00    5.00    --   58.00  74.00 -86.98   31
 15  \w     27.00  54.00   1.00    5.00    --   58.00  74.00-173.80   27
 16  \w     32.00  69.00   1.00    5.00    --   62.00  73.00  -0.65   37
 17  \w     32.00  71.00   1.00    5.00    --   62.00  73.00  42.74   39
 18  \w     33.00  69.00   1.00    5.00    --   62.00  73.00 148.21   36
 19  \w     31.00  74.00   1.00    5.00    --   62.00  74.00 -55.53   43
 20  \w     72.00 134.00   1.00    5.00    --   62.00  73.00  42.74   62
 21  \w     37.00  64.00   1.00    5.00    --   66.00  73.00-141.05   27
 22  \w     35.00  61.00   1.00    5.00    --   66.00  74.00-163.63   26
 23  \w    104.00 131.00   1.00    5.00    --   66.00  73.00-141.05   27
 24  \w     46.00  73.00   1.00    5.00    --   70.00  65.00 -61.04   27
 25  \w     49.00  82.00   1.00   20.00    --   74.00  69.00 102.19   33
 26  \w     51.00  77.00   1.00   20.00    --   78.00  61.00 -91.97   26
 27  \w     52.00  81.00   1.00   20.00    --   78.00  60.00  25.66   29
 28  \w     53.00  89.00   1.00   20.00    --   82.00  73.00 143.20   36
 29  \w    107.00 153.00   1.00   20.00    --   82.00  71.00  80.14   46
 30  \w     52.00  78.00   1.00   20.00    --   82.00  71.00  80.14   26
 31  \w     66.00 158.00   1.00   20.00    --   94.00  66.00  25.31   92
 32  \w    117.00 145.00   1.00   20.00    --  101.13  61.00-120.00   28
 33  \w     76.00 103.00   1.00   20.00    --  101.13  61.00-120.00   27
 34  \w     25.00 106.00   1.00   20.00    --  101.13 -94.00 -90.00   81
 35  \w     66.00  93.00   1.00   20.00    --  101.13 -61.00  90.00   27
 36  \w     74.00 166.00   1.00   20.00    --  101.13  61.00 120.00   92
 37  \w     28.00  56.00   1.00   20.00    --  101.13 -30.00-120.00   28
 38  \w     74.00 169.00   1.00   20.00    --  101.13  61.00 -90.00   95
 39  \w     75.00 137.00   1.00   20.00    --  101.13  61.00-180.00   62
 40  \w    129.00 171.00   1.00   20.00    --  101.13 125.00 120.00   42
 41  \w     36.00  71.00   1.00   20.00    --  101.13 -45.00 -90.00   35
 42  \w    122.00 147.00   1.00   20.00    --  101.13  61.00 -30.00   25
 43  \w     19.00  97.00   1.00   20.00    --  101.13 -94.00-150.00   78
 44  \w     74.00 120.00   1.00   20.00    --  101.13  61.00 -30.00   46
 45  \w    123.00 170.00   1.00   20.00    --  101.13  61.00 150.00   47
 46  \w     74.00 171.00   1.00   20.00    --  101.13  61.00-150.00   97
 47  \w     31.00 113.00   1.00   20.00    --  101.13-125.00  90.00   82
 48  \w     75.00 103.00   1.00   20.00    --  101.13  61.00 150.00   28
 49  \w    119.00 169.00   1.00   20.00    --  101.13  61.00 -60.00   50
 50  \w     74.00 103.00   1.00   20.00    --  101.13  61.00 -60.00   29
 51  \w    112.00 153.00   1.00   20.00    --  101.13  61.00  60.00   41
 52  \w     75.00 130.00   1.00   20.00    --  101.13  61.00  90.00   55
 53  \w     75.00 107.00   1.00   20.00    --  101.13  61.00  60.00   32
 54  \w     18.00 105.00   1.00   20.00    --  101.13 -94.00 120.00   87
 55  \w    118.00 170.00   1.00   20.00    --  101.13  61.00   0.00   52
 56  \w     74.00 115.00   1.00   20.00    --  101.13  61.00   0.00   41
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Titan 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      -0.1678219000
_diffrn_orient_matrix_UB_12      -0.0288958000
_diffrn_orient_matrix_UB_13      -0.0606608000
_diffrn_orient_matrix_UB_21      0.0153966000
_diffrn_orient_matrix_UB_22      0.0604706000
_diffrn_orient_matrix_UB_23      -0.0771570000
_diffrn_orient_matrix_UB_31      -0.0050936000
_diffrn_orient_matrix_UB_32      -0.1193185000
_diffrn_orient_matrix_UB_33      -0.0926571000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0280
_diffrn_reflns_av_unetI/netI     0.0188
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            23255
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.255
_diffrn_reflns_theta_min         3.873
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    0.962
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.712
_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    1.098
_exptl_crystal_description       block
_exptl_crystal_F_000             516
_exptl_crystal_size_max          0.158
_exptl_crystal_size_mid          0.149
_exptl_crystal_size_min          0.071
_refine_diff_density_max         0.211
_refine_diff_density_min         -0.163
_refine_diff_density_rms         0.028
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     375
_refine_ls_number_reflns         5573
_refine_ls_number_restraints     401
_refine_ls_restrained_S_all      1.005
_refine_ls_R_factor_all          0.0435
_refine_ls_R_factor_gt           0.0381
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0563P)^2^+0.3126P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1005
_refine_ls_wR_factor_ref         0.1057
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4918
_reflns_number_total             5573
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01414_si_005.cif
_cod_data_source_block           tbltbv
_cod_depositor_comments
'Adding full bibliography for 4517604--4517617.cif.'
_cod_original_cell_volume        1447.74(6)
_cod_database_code               4517609
_nottingham_internal_coll_name   TBLTBV
_nottingham_internal_coll_number 18404
_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   29/08/2019
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_process_date 02/09/2019
_nottingham_internal_process_user pczspa
_nottingham_internal_solution_date 07/11/2019
_nottingham_internal_solution_user pczspa
_nottingham_internal_refinement_date 07/11/2019
_nottingham_internal_refinement_user pczspa
_nottingham_internal_validation_date 07/11/2019
_nottingham_internal_validation_user pczspa
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C36H39P
_chemical_oxdiff_usercomment
'TBLTBV #18404 GVA-1701 in fomblin film on a micromount for TB/LTB'
_shelx_estimated_absorpt_t_max   0.935
_shelx_estimated_absorpt_t_min   0.863
_reflns_odcompleteness_completeness 99.65
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C30A-C29 \\sim C30-C29
 with sigma of 0.02
3. Restrained planarity
 C30A, C35A, C34A, C33A, C32A, C31A
 with sigma of 0.1
 C31A, C30A, C35A, C29
 with sigma of 0.1
 C29, C30, C31, C35
 with sigma of 0.1
 C30, C31, C32, C33, C34, C35
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C30 \\sim C35 \\sim C34 \\sim C33 \\sim C32 \\sim C31 \\sim C19 \\sim C20 \\sim
C21 \\sim C22 \\sim C23 \\sim C24: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C30A
\\sim C35A \\sim C34A \\sim C33A \\sim C32A \\sim C31A: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
5. Rigid body (RIGU) restrains
 C30, C31, C32, C33, C34, C35, C21, C22, C23, C24, C19, C20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C29, C30, C31, C32, C33, C34, C35, C30A, C35A, C34A, C33A, C32A, C31A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{C30, C35, C34, C33, C32, C31} sigma for 1-2: 0.02, 1-3: 0.04
as
{C30, C31, C32, C33, C34, C35}
{C30, C31, C32, C33, C34, C35} sigma for 1-2: 0.02, 1-3: 0.04
{C30, C35, C34, C33, C32, C31} sigma for 1-2: 0.02, 1-3: 0.04
as
{C30A, C35A, C34A, C33A, C32A, C31A}
7. Others
 Sof(H29C)=Sof(H29D)=Sof(C30A)=Sof(C35A)=Sof(H35A)=Sof(C34A)=Sof(H34A)=
 Sof(C33A)=Sof(H33A)=Sof(C32A)=Sof(H32A)=Sof(C31A)=Sof(H31A)=1-FVAR(1)
 Sof(H29A)=Sof(H29B)=Sof(C30)=Sof(C31)=Sof(H31)=Sof(C32)=Sof(H32)=Sof(C33)=
 Sof(H33)=Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35)=FVAR(1)
8.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C18(H18A,H18B), C28(H28A,H28B), C29(H29A,H29B), C29(H29C,H29D)
8.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C31(H31), C32(H32),
  C33(H33), C34(H34), C35(H35), C35A(H35A), C34A(H34A), C33A(H33A), C32A(H32A),
 C31A(H31A)
8.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C)
;
_shelx_res_checksum              59831
_shelx_hkl_checksum              12373
_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 1.569
_oxdiff_exptl_absorpt_empirical_full_min 0.661