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_4517614
_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         '2(C22 H31 Au Cl P), 0.5(C6 H12)'
_chemical_formula_sum            'C47 H68 Au2 Cl2 P2'
_chemical_formula_weight         1159.78
_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             2019-11-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                78.850(3)
_cell_angle_beta                 81.860(2)
_cell_angle_gamma                78.924(3)
_cell_formula_units_Z            2
_cell_length_a                   10.0872(3)
_cell_length_b                   14.0744(6)
_cell_length_c                   16.7016(5)
_cell_measurement_reflns_used    20833
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      34.6710
_cell_measurement_theta_min      3.0660
_cell_volume                     2269.59(14)
_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 10.3613
_diffrn_detector_type            'Agilent Diffraction Atlas detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.936
_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    -80.00 -41.00   1.00   40.00    --  -22.07 129.00-162.37   39
  2  \w    -80.00 -38.00   1.00   40.00    --  -22.07 129.00 106.02   42
  3  \w    -50.00  39.00   1.00   40.00    --   23.01 -38.00 150.00   89
  4  \w     -4.00  87.00   1.00   40.00    --   23.01  77.00 -60.00   91
  5  \w     -3.00  92.00   1.00   40.00    --   23.01  77.00-180.00   95
  6  \w    -37.00  40.00   1.00   40.00    --   23.01 -25.00-143.00   77
  7  \w     -3.00  91.00   1.00   40.00    --   23.01  77.00  60.00   94
  8  \w    -23.00  35.00   1.00   40.00    --   23.01 -38.00   0.00   58
  9  \w    -50.00  39.00   1.00   40.00    --   23.01 -38.00  60.00   89
 10  \w    -46.00  38.00   1.00   40.00    --   23.01 -38.00 -60.00   84
 11  \w     48.00  82.00   1.00   40.00    --   23.01-131.00 112.23   34
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Atlas'
_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      0.0702171000
_diffrn_orient_matrix_UB_12      -0.0192849000
_diffrn_orient_matrix_UB_13      -0.0066033000
_diffrn_orient_matrix_UB_21      0.0161688000
_diffrn_orient_matrix_UB_22      0.0416134000
_diffrn_orient_matrix_UB_23      0.0121733000
_diffrn_orient_matrix_UB_31      -0.0017826000
_diffrn_orient_matrix_UB_32      -0.0247598000
_diffrn_orient_matrix_UB_33      0.0412820000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0359
_diffrn_reflns_av_unetI/netI     0.0395
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.936
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            64649
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.936
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         35.063
_diffrn_reflns_theta_min         2.994
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    6.676
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.366
_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    1.697
_exptl_crystal_description       plate
_exptl_crystal_F_000             1144
_exptl_crystal_size_max          0.178
_exptl_crystal_size_mid          0.143
_exptl_crystal_size_min          0.036
_refine_diff_density_max         1.228
_refine_diff_density_min         -1.663
_refine_diff_density_rms         0.131
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     631
_refine_ls_number_reflns         18791
_refine_ls_number_restraints     656
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0462
_refine_ls_R_factor_gt           0.0285
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0163P)^2^+0.7704P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0483
_refine_ls_wR_factor_ref         0.0539
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15000
_reflns_number_total             18791
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01414_si_006.cif
_cod_data_source_block           tbltbx
_cod_depositor_comments
'Adding full bibliography for 4517604--4517617.cif.'
_cod_database_code               4517614
_nottingham_internal_coll_name   TBLTBX
_nottingham_internal_coll_number 18426
_nottingham_internal_coll_client TB/LTB
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time 40.00
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczspa
_nottingham_internal_coll_date   07/10/2019
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'SN, XDA 017-09'
_nottingham_internal_process_date 08/10/2019
_nottingham_internal_process_user pczspa
_nottingham_internal_solution_date 08/10/2019
_nottingham_internal_solution_user pczspa
_nottingham_internal_refinement_date 12/11/2019
_nottingham_internal_refinement_user pczspa
_nottingham_internal_validation_date 12/11/2019
_nottingham_internal_validation_user pczspa
_nottingham_internal_archive_date 12/11/2019
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C28H43AuCl1P
_chemical_oxdiff_usercomment
'TBLTBX #18426 SN-1534 TB/LTB MICROMOUNT IN FOMBLIN'
_shelx_estimated_absorpt_t_max   0.795
_shelx_estimated_absorpt_t_min   0.383
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     33.07
_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 C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Au1B \\sim Au1C: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
P3B \\sim P3C: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
P3B \\sim C16B \\sim C17B \\sim C18B \\sim C19B \\sim C20B \\sim C21B \\sim
C22B \\sim C23B \\sim C24B \\sim C25B \\sim P3C \\sim C16C \\sim C17C \\sim
C18C \\sim C19C \\sim C20C \\sim C21C \\sim C22C \\sim C23C \\sim C24C \\sim
C25C: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Cl2B \\sim Cl2C: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
Uanis(Cl2C) = Uanis(Cl2B)
3. Rigid body (RIGU) restrains
 P3B, C16B, C17B, C18B, C19B, C20B, C21B, C22B, C23B, C24B, C25B, P3C, C16C,
 C17C, C18C, C19C, C20C, C21C, C22C, C23C, C24C, C25C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1D, C2D, C3D, C4D, C5D, C6D, C2E, C1E, C6E, C3E, C5E, C4E
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Same fragment restrains
{C16A, C17A, C18A, C19A, C20A} sigma for 1-2: 0.02, 1-3: 0.04
{C16A, C18A, C17A, C19A, C20A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C21A, C22A, C23A, C24A, C25A}
{C16A, C17A, C18A, C19A, C20A} sigma for 1-2: 0.02, 1-3: 0.04
{C16A, C18A, C17A, C19A, C20A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C16B, C17B, C18B, C19B, C20B}
{C16A, C17A, C18A, C19A, C20A} sigma for 1-2: 0.02, 1-3: 0.04
{C16A, C18A, C17A, C19A, C20A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C21B, C22B, C23B, C24B, C25B}
{C16A, C17A, C18A, C19A, C20A} sigma for 1-2: 0.02, 1-3: 0.04
{C16A, C18A, C17A, C19A, C20A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C16C, C17C, C18C, C19C, C20C}
{C16A, C17A, C18A, C19A, C20A} sigma for 1-2: 0.02, 1-3: 0.04
{C16A, C18A, C17A, C19A, C20A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C21C, C22C, C23C, C24C, C25C}
5. Others
 Sof(Au1C)=Sof(P3C)=Sof(C16C)=Sof(C17C)=Sof(H4AA)=Sof(H5AA)=Sof(H6AA)=
 Sof(C18C)=Sof(H7AA)=Sof(H8AA)=Sof(H9AA)=Sof(C19C)=Sof(H0BA)=Sof(H1BA)=
 Sof(C20C)=Sof(H2BA)=Sof(H3BA)=Sof(H4BA)=Sof(C21C)=Sof(C22C)=Sof(H5BA)=
 Sof(H6BA)=Sof(H7BA)=Sof(C23C)=Sof(H8BA)=Sof(H9BA)=Sof(H0CA)=Sof(C24C)=
 Sof(H1CA)=Sof(H2CA)=Sof(C25C)=Sof(H3CA)=Sof(H4CA)=Sof(H5CA)=Sof(Cl2C)=1-FVAR(1)
 Sof(Au1B)=Sof(Cl2B)=Sof(P3B)=Sof(C16B)=Sof(C17B)=Sof(HI)=Sof(HJ)=Sof(HK)=
 Sof(C18B)=Sof(HL)=Sof(HM)=Sof(HN)=Sof(C19B)=Sof(HO)=Sof(HP)=Sof(C20B)=Sof(HQ)=
 Sof(HR)=Sof(HS)=Sof(C21B)=Sof(C22B)=Sof(HT)=Sof(HU)=Sof(HV)=Sof(C23B)=Sof(HW)=
 Sof(HX)=Sof(HY)=Sof(C24B)=Sof(HZ)=Sof(H0AA)=Sof(C25B)=Sof(H1AA)=Sof(H2AA)=
 Sof(H3AA)=FVAR(1)
 Sof(C2E)=Sof(H8DA)=Sof(H9DA)=Sof(C1E)=Sof(H0EA)=Sof(H1EA)=Sof(C6E)=Sof(H2EA)=
 Sof(H3EA)=Sof(C3E)=Sof(H4EA)=Sof(H5EA)=Sof(C5E)=Sof(H6EA)=Sof(H7EA)=Sof(C4E)=
 Sof(H8EA)=Sof(H9EA)=0.5*(1-FVAR(3))
 Sof(C1D)=Sof(H6CA)=Sof(H7CA)=Sof(C2D)=Sof(H8CA)=Sof(H9CA)=Sof(C3D)=Sof(H0DA)=
 Sof(H1DA)=Sof(C4D)=Sof(H2DA)=Sof(H3DA)=Sof(C5D)=Sof(H4DA)=Sof(H5DA)=Sof(C6D)=
 Sof(H6DA)=Sof(H7DA)=0.5*FVAR(3)
 Uiso(C2E)=Uiso(C1E)=Uiso(C6E)=Uiso(C3E)=Uiso(C5E)=Uiso(C4E)=FVAR(3)
6.a Free rotating group:
 C1D(C2D,C3D,C4D,C5D,C6D), C2E(C1E,C6E,C3E,C5E,C4E)
6.b Secondary CH2 refined with riding coordinates:
 C19A(H19A,H19B), C24A(H24A,H24B), C19B(HO,HP), C24B(HZ,H0AA), C19C(H0BA,H1BA),
  C24C(H1CA,H2CA), C1D(H6CA,H7CA), C2D(H8CA,H9CA), C3D(H0DA,H1DA), C4D(H2DA,
 H3DA), C5D(H4DA,H5DA), C6D(H6DA,H7DA), C2E(H8DA,H9DA), C1E(H0EA,H1EA),
 C6E(H2EA,H3EA), C3E(H4EA,H5EA), C5E(H6EA,H7EA), C4E(H8EA,H9EA)
6.c Aromatic/amide H refined with riding coordinates:
 C6A(H6A), C7A(H7A), C8A(H8A), C9A(H9A), C11A(H11A), C12A(H12A), C13A(H13A),
 C14A(H14A), C15A(H15A), C6B(H), C7B(HA), C8B(HB), C9B(HC), C11B(HD), C12B(HE),
 C13B(HF), C14B(HG), C15B(HH)
6.d Idealised Me refined as rotating group:
 C17A(H17A,H17B,H17C), C18A(H18A,H18B,H18C), C20A(H20A,H20B,H20C), C22A(H22A,
 H22B,H22C), C23A(H23A,H23B,H23C), C25A(H25A,H25B,H25C), C17B(HI,HJ,HK),
 C18B(HL,HM,HN), C20B(HQ,HR,HS), C22B(HT,HU,HV), C23B(HW,HX,HY), C25B(H1AA,H2AA,
 H3AA), C17C(H4AA,H5AA,H6AA), C18C(H7AA,H8AA,H9AA), C20C(H2BA,H3BA,H4BA),
 C22C(H5BA,H6BA,H7BA), C23C(H8BA,H9BA,H0CA), C25C(H3CA,H4CA,H5CA)
;
_shelx_res_checksum              4683
_shelx_hkl_checksum              26224
_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 1.598
_oxdiff_exptl_absorpt_empirical_full_min 0.674