Triaryl-Like MONO-, BIS-, and TRISKITPHOS Phosphines: Synthesis, Solution NMR Studies, and a Comparison in Gold-Catalyzed Carbon‒Heteroatom Bond Forming 5-exo-dig and 6-endo-dig Cyclizations
Doherty, Simon; Knight, Julian G.; Perry, Daniel O.; Ward, Nicholas A. B.; Bittner, Dror M.; McFarlane, William; Wills, Corinne; Probert, Michael R.; Organometallics 35 (2016) 1265–; doi:10.1021/acs.organomet.6b00146

data_4088515
_publ_section_title
;
 Triaryl-Like MONO-, BIS-, and TRISKITPHOS Phosphines: Synthesis, Solution
 NMR Studies, and a Comparison in Gold-Catalyzed Carbon--Heteroatom Bond
 Forming 5-exo-dig and 6-endo-dig Cyclizations
;
_journal_issue                   9
_journal_name_full               Organometallics
_journal_page_first              1265
_journal_paper_doi               10.1021/acs.organomet.6b00146
_journal_volume                  35
_journal_year                    2016
_chemical_formula_moiety         'C66 H45 Au Cl P, 0.5(C H Cl3), 3(C H4 O)'
_chemical_formula_sum            'C69.5 H57.5 Au Cl2.5 O3 P'
_chemical_formula_weight         1257.21
_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     direct
_audit_creation_date             2015-07-17
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3151 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90.812(2)
_cell_angle_beta                 97.791(2)
_cell_angle_gamma                114.377(3)
_cell_formula_units_Z            2
_cell_length_a                   11.9837(4)
_cell_length_b                   13.0538(4)
_cell_length_c                   19.8023(6)
_cell_measurement_reflns_used    18847
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      29.0208
_cell_measurement_theta_min      2.8011
_cell_volume                     2787.07(17)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.0
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3968
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.843
_diffrn_measurement_details
;
  1 omega  -74.00   25.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -10.5696  -77.0000    0.0000 99

  2 omega  -13.00   88.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       12.2102   38.0000  -60.0000 101

  3 omega  -17.00   89.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       12.2102   38.0000 -180.0000 106

  4 omega  -44.00   28.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       12.2102  -38.0000 -150.0000 72

  5 omega  -52.00   49.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       14.0000  -65.0000   21.0000 101

  6 omega  -57.00   47.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       14.0000  -67.0000  141.0000 104

  7 omega   13.00   70.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       14.0000 -119.0000  -43.0000 57
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0388663000
_diffrn_orient_matrix_UB_12      -0.0080819000
_diffrn_orient_matrix_UB_13      -0.0318209000
_diffrn_orient_matrix_UB_21      0.0498712000
_diffrn_orient_matrix_UB_22      0.0419714000
_diffrn_orient_matrix_UB_23      -0.0132944000
_diffrn_orient_matrix_UB_31      0.0181449000
_diffrn_orient_matrix_UB_32      -0.0418737000
_diffrn_orient_matrix_UB_33      -0.0112097000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0323
_diffrn_reflns_av_unetI/netI     0.0369
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.843
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            41654
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.843
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.021
_diffrn_reflns_theta_min         2.801
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.837
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84127
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.498
_exptl_crystal_description       block
_exptl_crystal_F_000             1270
_exptl_crystal_size_max          0.4857
_exptl_crystal_size_mid          0.3635
_exptl_crystal_size_min          0.3063
_refine_diff_density_max         1.003
_refine_diff_density_min         -1.095
_refine_diff_density_rms         0.101
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     729
_refine_ls_number_reflns         12527
_refine_ls_number_restraints     673
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0392
_refine_ls_R_factor_gt           0.0326
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0340P)^2^+5.6262P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0782
_refine_ls_wR_factor_ref         0.0822
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11269
_reflns_number_total             12527
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00146_si_002.cif
_cod_data_source_block           jgk73
_cod_original_cell_volume        2787.07(15)
_cod_original_formula_sum        'C69.50 H57.50 Au Cl2.50 O3 P'
_cod_database_code               4088515
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C66 H13 P Au Cl'
_reflns_odcompleteness_completeness 98.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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 O(H) groups, All O(H,H) groups
2. Restrained distances
 O1M-C1M \\sim O1M-C5M
 with sigma of 0.02
 O1M-C1M \\sim O2M_$2-C2M_$2 \\sim O3M_$1-C3M_$1
 with sigma of 0.02
 O3M-C3M \\sim O4M-C4M
 with sigma of 0.02
 Cl3S-C1S \\sim Cl1S-C1S \\sim Cl2S-C1S
 with sigma of 0.02
 Cl1S-C1S \\sim Cl2S-C1S \\sim Cl3S-C1S
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C1M) = Uanis(C5M)
Uanis(C3M) = Uanis(C4M)
Uanis(O3M) = Uanis(O4M)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: Cl1S(0.5) Cl2S(0.5) Cl3S(0.5) H1M(0.7326) H1MA(0.2674)
 O3M(0.84623) H3M(0.84623) O4M(0.15377) H4M(0.15377) C1M(0.7326) H1MB(0.7326)
 H1MC(0.7326) H1MD(0.7326) C1S(0.5) H1S(0.5) C3M(0.84623) H3MA(0.84623)
 H3MB(0.84623) H3MC(0.84623) C4M(0.15377) H4MA(0.15377) H4MB(0.15377)
 H4MC(0.15377) C5M(0.2674) H5MA(0.2674) H5MB(0.2674) H5MC(0.2674)
6.a Ternary CH refined with riding coordinates:
 C1S(H1S), C2(H2), C9(H9), C24(H24), C31(H31), C46(H46), C53(H53)
6.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C11(H11), C12(H12), C13(H13), C14(H14),
 C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C26(H26), C27(H27), C28(H28),
  C29(H29), C33(H33), C34(H34), C35(H35), C36(H36), C40(H40), C41(H41),
 C42(H42), C43(H43), C44(H44), C48(H48), C49(H49), C50(H50), C51(H51), C55(H55),
  C56(H56), C57(H57), C58(H58), C62(H62), C63(H63), C64(H64), C65(H65), C66(H66)
6.c Tetrahedral OH refined with riding coordinates:
 O1M(H1M), O1M(H1MA)
6.d Idealised Me refined as rotating group:
 C1M(H1MB,H1MC,H1MD), C2M(H2MA,H2MB,H2MC), C3M(H3MA,H3MB,H3MC), C4M(H4MA,H4MB,
 H4MC), C5M(H5MA,H5MB,H5MC)
6.e Idealised tetrahedral OH refined as rotating group:
 O2M(H2M), O3M(H3M), O4M(H4M)
;
_shelx_res_checksum              30688
_shelx_hkl_checksum              1552
_olex2_submission_special_instructions 'No special instructions were received'