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_4517605
_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         'C12 H28 P, C F3 O3 S'
_chemical_formula_sum            'C13 H28 F3 O3 P S'
_chemical_formula_weight         352.38
_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   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-10-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 106.967(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.8317(4)
_cell_length_b                   22.6453(9)
_cell_length_c                   9.2451(6)
_cell_measurement_reflns_used    3723
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      73.7960
_cell_measurement_theta_min      3.8920
_cell_volume                     1768.51(17)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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 0.987
_diffrn_measured_fraction_theta_max 0.955
_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   -112.00 -19.00   1.00    2.00    --  -42.81 -57.00  30.00   93
  2  \w    -42.00  -1.00   1.00    2.00    --  -42.81  38.00 -30.00   41
  3  \w     31.00  85.00   1.00    2.00    --   42.81-125.00-150.00   54
  4  \w     92.00 174.00   1.00    8.00    --  103.00  30.00-150.00   82
  5  \w     97.00 163.00   1.00    8.00    --  103.00  45.00-120.00   66
  6  \w     30.00  78.00   1.00    8.00    --  103.00 -30.00  90.00   48
  7  \w     29.00 110.00   1.00    8.00    --  103.00 -94.00 120.00   81
  8  \w     40.00 127.00   1.00    8.00    --  103.00 -61.00 150.00   87
;
_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      0.0117432000
_diffrn_orient_matrix_UB_12      0.0677972000
_diffrn_orient_matrix_UB_13      0.0107708000
_diffrn_orient_matrix_UB_21      0.1808924000
_diffrn_orient_matrix_UB_22      -0.0047800000
_diffrn_orient_matrix_UB_23      0.0687201000
_diffrn_orient_matrix_UB_31      0.0201865000
_diffrn_orient_matrix_UB_32      0.0025718000
_diffrn_orient_matrix_UB_33      -0.1598525000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0431
_diffrn_reflns_av_unetI/netI     0.0363
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            6294
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.624
_diffrn_reflns_theta_min         5.370
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    2.814
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.349
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.323
_exptl_crystal_description       block
_exptl_crystal_F_000             752
_exptl_crystal_size_max          0.326
_exptl_crystal_size_mid          0.242
_exptl_crystal_size_min          0.142
_refine_diff_density_max         0.931
_refine_diff_density_min         -0.469
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     333
_refine_ls_number_reflns         3407
_refine_ls_number_restraints     1050
_refine_ls_restrained_S_all      1.007
_refine_ls_R_factor_all          0.0866
_refine_ls_R_factor_gt           0.0823
_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^)+(0.1680P)^2^+4.0663P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2221
_refine_ls_wR_factor_ref         0.2282
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3113
_reflns_number_total             3407
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01414_si_010.cif
_cod_data_source_block           vjmlbe
_cod_depositor_comments
'Adding full bibliography for 4517604--4517617.cif.'
_cod_database_code               4517605
_nottingham_internal_coll_name   VJMLBE
_nottingham_internal_coll_number 17806
_nottingham_internal_coll_client VJM/LB
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '8.00, 2.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczajb
_nottingham_internal_coll_date   02/08/2018
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_process_date 03/08/2018
_nottingham_internal_process_user pczajb
_nottingham_internal_solution_date 08/10/2019
_nottingham_internal_solution_user pczspa
_nottingham_internal_refinement_date 08/10/2019
_nottingham_internal_refinement_user pczspa
_nottingham_internal_validation_date 08/10/2019
_nottingham_internal_validation_user pczspa
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C13 H28 F3 O3 P1 S1'
_chemical_oxdiff_usercomment
'VJMLBE #17806 GVA-1470 IN FOMBLIN FILM ON MICROMOUNT FOR VJM/LB'
_reflns_odcompleteness_completeness 99.02
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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, All P(H,H) groups
2. Restrained distances
 P1C-C2C \\sim P1B-C2B \\sim P1C-C2A \\sim P1B-C2A
 with sigma of 0.01
 P1C-H1BA \\sim P1B-H1BA \\sim P1C-H1BB \\sim P1B-H1BB
 with sigma of 0.02
 P1C-H1BA \\sim P1B-H1BA \\sim P1B-H1BB \\sim P1C-H1BB
 with sigma of 0.02
 P1C-H1CA \\sim P1B-H1BA \\sim P1B-H1BB \\sim P1C-H1CB
 with sigma of 0.02
 H1CB-H1CA \\sim H1BB-H1BA
 with sigma of 0.02
 C2A-H1BA \\sim C2A-H1BB \\sim C2A-H1CB \\sim C2A-H1CA \\sim C2B-H1BA \\sim
C2B-H1BB \\sim C2C-H1CB ~
 C2C-H1CA
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2.5A with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(S14B) = Uanis(S14A)
Uanis(C18A) = Uanis(C18B)
Uanis(P1C) = Uanis(P1B)
4. Rigid body (RIGU) restrains
 C2A, C3A, C4A, C5A, C6A, C7A, C2B, C3B, C4B, C5B, C6B, C7B, C2C, C3C, C4C,
 C5C, C6C, C7C, C18B, C18A, S14B, S14A, O15B, O16B, O17B, O15A, O16A, O17A,
 F19B, F20B, F21B, F19A, F20A, F21A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C2A, C4A, C3A, C5A, C7A, C6A} sigma for 1-2: 0.01, 1-3: 0.02
as
{C2A, C3A, C4A, C5A, C6A, C7A}
{C2A, C4A, C3A, C5A, C7A, C6A} sigma for 1-2: 0.01, 1-3: 0.02
{C2A, C3A, C4A, C5A, C6A, C7A} sigma for 1-2: 0.01, 1-3: 0.02
as
{C2B, C3B, C4B, C5B, C6B, C7B}
{C2A, C3A, C4A, C5A, C6A, C7A} sigma for 1-2: 0.01, 1-3: 0.02
{C2A, C4A, C3A, C5A, C7A, C6A} sigma for 1-2: 0.01, 1-3: 0.02
as
{C2C, C3C, C4C, C5C, C6C, C7C}
{S14A, O17A, O15A, O16A, C18A, F21A, F19A, F20A} sigma for 1-2: 0.01, 1-3: 0.02
{S14A, O15A, O16A, O17A, C18A, F19A, F20A, F21A} sigma for 1-2: 0.01, 1-3: 0.02
{S14A, O16A, O17A, O15A, C18A, F20A, F21A, F19A} sigma for 1-2: 0.01, 1-3: 0.02
as
{S14B, O15B, O16B, O17B, C18B, F19B, F20B, F21B}
{S14A, O16A, O17A, O15A, C18A, F20A, F21A, F19A} sigma for 1-2: 0.01, 1-3: 0.02
{S14A, O17A, O15A, O16A, C18A, F21A, F19A, F20A} sigma for 1-2: 0.01, 1-3: 0.02
as
{S14A, O15A, O16A, O17A, C18A, F19A, F20A, F21A}
6. Others
 Sof(S14A)=Sof(O15A)=Sof(O16A)=Sof(O17A)=Sof(C18A)=Sof(F19A)=Sof(F20A)=
 Sof(F21A)=1-FVAR(1)
 Sof(S14B)=Sof(O15B)=Sof(O16B)=Sof(O17B)=Sof(C18B)=Sof(F19B)=Sof(F20B)=
 Sof(F21B)=FVAR(1)
 Sof(P1C)=Sof(H1CA)=Sof(H1CB)=Sof(C2C)=Sof(C3C)=Sof(H3CA)=Sof(H3CB)=Sof(H3CC)=
 Sof(C4C)=Sof(H4CA)=Sof(H4CB)=Sof(H4CC)=Sof(C5C)=Sof(H5C)=Sof(C6C)=Sof(H6CA)=
 Sof(H6CB)=Sof(H6CC)=Sof(C7C)=Sof(H7CA)=Sof(H7CB)=Sof(H7CC)=1-FVAR(2)
 Sof(P1B)=Sof(H1BA)=Sof(H1BB)=Sof(C2B)=Sof(C3B)=Sof(H3BA)=Sof(H3BB)=Sof(H3BC)=
 Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(H4BC)=Sof(C5B)=Sof(H5B)=Sof(C6B)=Sof(H6BA)=
 Sof(H6BB)=Sof(H6BC)=Sof(C7B)=Sof(H7BA)=Sof(H7BB)=Sof(H7BC)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C5A(H5A), C5B(H5B), C5C(H5C)
7.b Idealised Me refined as rotating group:
 C3A(H3AA,H3AB,H3AC), C4A(H4AA,H4AB,H4AC), C6A(H6AA,H6AB,H6AC), C7A(H7AA,H7AB,
 H7AC), C3B(H3BA,H3BB,H3BC), C4B(H4BA,H4BB,H4BC), C6B(H6BA,H6BB,H6BC), C7B(H7BA,
 H7BB,H7BC), C3C(H3CA,H3CB,H3CC), C4C(H4CA,H4CB,H4CC), C6C(H6CA,H6CB,H6CC),
 C7C(H7CA,H7CB,H7CC)
;
_shelx_res_checksum              65156
_shelx_hkl_checksum              9233
_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:
;
_oxdiff_exptl_absorpt_empirical_full_max 1.336
_oxdiff_exptl_absorpt_empirical_full_min 0.755