Tuning reactivity through implementation of the HSAB concept in oxygen- and sulphur-bridged Al/P and Ga/P FLPs.
Buth, Julian; Vishnevskiy, Yury V.; Lamm, Jan-Hendrik; Neumann, Beate; Stammler, Hans-Georg; Mitzel, Norbert W.; Dalton transactions (Cambridge, England : 2003) 55 (2026) 2691–2701; doi:10.1039/d6dt00151c

data_7720117
_publ_section_title
;
 Tuning reactivity through implementation of the HSAB concept in oxygen-
 and sulphur-bridged Al/P and Ga/P FLPs.
;
_journal_issue                   6
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              2691
_journal_page_last               2701
_journal_paper_doi               10.1039/d6dt00151c
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C22 H56 Ga P S Si4'
_chemical_formula_sum            'C22 H56 Ga P S Si4'
_chemical_formula_weight         565.77
_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
_audit_creation_date             2024-06-28
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-11-17 deposited with the CCDC.	2026-01-21 downloaded from the CCDC.
;
_cell_angle_alpha                107.069(2)
_cell_angle_beta                 97.760(2)
_cell_angle_gamma                90.634(2)
_cell_formula_units_Z            2
_cell_length_a                   9.4107(2)
_cell_length_b                   13.3305(4)
_cell_length_c                   13.9075(4)
_cell_measurement_reflns_used    35729
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      34.5390
_cell_measurement_theta_min      3.7500
_cell_volume                     1650.19(8)
_computing_cell_refinement       'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.127a 64-bit (release 16-06-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1773
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.964
_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    -68.00  15.00   1.00    5.00    --  -27.29 101.00 -76.00   83
  2  \w    -15.00  68.00   1.00    5.00    --   27.45-101.00 179.00   83
  3  \w   -102.00  -3.00   1.00    5.00    --  -27.29 -38.00 150.00   99
  4  \w   -106.00 -25.00   1.00    5.00    --  -27.29 160.00 -60.31   81
  5  \w   -103.00 -20.00   1.00    5.00    --  -27.29 153.00-175.97   83
  6  \w   -102.00  -3.00   1.00    5.00    --  -27.29 -38.00 150.00   99
  7  \w    -68.00  15.00   1.00    5.00    --  -27.29 101.00 -76.00   83
  8  \w    -61.00 116.00   1.00    5.00    --   27.45   0.00-180.00  177
  9  \w     -1.00 101.00   1.00    5.00    --   27.45  57.00 -30.00  102
 10  \w     -1.00 101.00   1.00    5.00    --   27.45  57.00  90.00  102
 11  \w     -5.00  42.00   1.00    5.00    --   27.45  77.00  30.00   47
 12  \w     -5.00  42.00   1.00    5.00    --   27.45  77.00-180.00   47
 13  \w    -47.00  52.00   1.00    5.00    --   27.45 -38.00  60.00   99
 14  \w     -1.00 101.00   1.00    5.00    --   27.45  57.00-150.00  102
 15  \w   -105.00 -23.00   1.00    5.00    --  -27.29 157.00  43.37   82
 16  \w    -42.00   5.00   1.00    5.00    --  -27.29 -77.00-150.00   47
 17  \w    -47.00  52.00   1.00    5.00    --   27.45 -38.00-180.00   99
 18  \w     39.00 116.00   1.00    5.00    --   27.45 178.00  90.00   77
 19  \w    -15.00  67.00   1.00    5.00    --   27.45 -99.00 -60.00   82
 20  \w      3.00 102.00   1.00    5.00    --   27.45  38.00  30.00   99
 21  \w    -14.00  67.00   1.00    5.00    --   27.45  19.00 -30.00   81
 22  \w     -5.00  42.00   1.00    5.00    --   27.45  77.00 120.00   47
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0203230000
_diffrn_orient_matrix_UB_12      -0.0317914000
_diffrn_orient_matrix_UB_13      0.0319560000
_diffrn_orient_matrix_UB_21      0.0258674000
_diffrn_orient_matrix_UB_22      0.0455688000
_diffrn_orient_matrix_UB_23      0.0403712000
_diffrn_orient_matrix_UB_31      -0.0687082000
_diffrn_orient_matrix_UB_32      0.0044452000
_diffrn_orient_matrix_UB_33      0.0160045000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0622
_diffrn_reflns_av_unetI/netI     0.0426
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            120880
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         36.700
_diffrn_reflns_theta_min         3.522
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.099
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.469
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.127a (Rigaku Oxford Diffraction, 2024)
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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.139
_exptl_crystal_description       irregular
_exptl_crystal_F_000             612
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.166
_refine_diff_density_min         -1.492
_refine_diff_density_rms         0.111
_refine_ls_extinction_coef       0.0032(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.115
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     480
_refine_ls_number_reflns         15842
_refine_ls_number_restraints     636
_refine_ls_restrained_S_all      1.133
_refine_ls_R_factor_all          0.0856
_refine_ls_R_factor_gt           0.0626
_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^)+(0.0250P)^2^+3.5715P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1265
_refine_ls_wR_factor_ref         0.1396
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12455
_reflns_number_total             15842
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00151c3.cif
_cod_data_source_block           GaSP
_cod_database_code               7720117
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C22 H56 Ga P S Si4'
_shelx_estimated_absorpt_t_max   0.879
_shelx_estimated_absorpt_t_min   0.693
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Si1B-C1 \\sim Si1A-C1
 with sigma of 0.02
 Si2A-C1 \\sim Si2B-C1
 with sigma of 0.02
 Si3B-C8 \\sim Si3A-C8
 with sigma of 0.02
 Si4A-C8 \\sim Si4B-C8
 with sigma of 0.02
 P1-C15A \\sim P1-C15B
 with sigma of 0.02
 P1-C19A \\sim P1-C19B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C15A \\sim C15B \\sim C16A \\sim C16B \\sim C17A \\sim C17B \\sim C18A \\sim
C18B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
C19A \\sim C19B \\sim C20A \\sim C20B \\sim C21A \\sim C21B \\sim C22A \\sim
C22B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
Si2A \\sim Si2B \\sim C5A \\sim C5B \\sim C6A \\sim C6B \\sim C7A \\sim C7B:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Si4A \\sim Si4B \\sim C12A \\sim C12B \\sim C13A \\sim C13B \\sim C14A \\sim
C14B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
Si3A \\sim Si3B \\sim C9A \\sim C9B \\sim C10A \\sim C10B \\sim C11A \\sim
C11B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
4. Rigid body (RIGU) restrains
 C15A, C15B, C16A, C16B, C17A, C17B, C18A, C18B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C19A, C19B, C20A, C20B, C21A, C21B, C22A, C22B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Si2A, Si2B, C5A, C5B, C6A, C6B, C7A, C7B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Si4A, Si4B, C12A, C12B, C13A, C13B, C14A, C14B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Si3A, Si3B, C9A, C9B, C10A, C10B, C11A, C11B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(Si1B)=Sof(Si2B)=Sof(Si3B)=Sof(Si4B)=Sof(H1B)=Sof(C2B)=Sof(H2BA)=Sof(H2BB)=
 Sof(H2BC)=Sof(C3B)=Sof(H3BA)=Sof(H3BB)=Sof(H3BC)=Sof(C4B)=Sof(H4BA)=Sof(H4BB)=
 Sof(H4BC)=Sof(C5B)=Sof(H5BA)=Sof(H5BB)=Sof(H5BC)=Sof(C6B)=Sof(H6BA)=Sof(H6BB)=
 Sof(H6BC)=Sof(C7B)=Sof(H7BA)=Sof(H7BB)=Sof(H7BC)=Sof(H8B)=Sof(C9B)=Sof(H9BA)=
 Sof(H9BB)=Sof(H9BC)=Sof(C10B)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C11B)=
 Sof(H11D)=Sof(H11E)=Sof(H11F)=Sof(C12B)=Sof(H12D)=Sof(H12E)=Sof(H12F)=
 Sof(C13B)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14B)=Sof(H14D)=Sof(H14E)=
 Sof(H14F)=Sof(C15B)=Sof(C16B)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C17B)=
 Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18B)=Sof(H18A)=Sof(H18B)=Sof(H18C)=
 Sof(C19B)=Sof(C20B)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C21B)=Sof(H21D)=
 Sof(H21E)=Sof(H21F)=Sof(C22B)=Sof(H22D)=Sof(H22E)=Sof(H22F)=1-FVAR(1)
 Sof(Si1A)=Sof(Si2A)=Sof(Si3A)=Sof(Si4A)=Sof(H1A)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=
 Sof(H2AC)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=
 Sof(H4AC)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=
 Sof(H6AC)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=Sof(H8A)=Sof(C9A)=Sof(H9AA)=
 Sof(H9AB)=Sof(H9AC)=Sof(C10A)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11A)=
 Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C12A)=Sof(H12A)=Sof(H12B)=Sof(H12C)=
 Sof(C13A)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14A)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=Sof(C15A)=Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C17A)=
 Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=
 Sof(C19A)=Sof(C20A)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C21A)=Sof(H21A)=
 Sof(H21B)=Sof(H21C)=Sof(C22A)=Sof(H22A)=Sof(H22B)=Sof(H22C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C1(H1A), C1(H1B), C8(H8A), C8(H8B)
6.b Me refined with riding coordinates:
 C2A(H2AA,H2AB,H2AC), C2B(H2BA,H2BB,H2BC), C3A(H3AA,H3AB,H3AC), C3B(H3BA,H3BB,
 H3BC), C4A(H4AA,H4AB,H4AC), C4B(H4BA,H4BB,H4BC), C5A(H5AA,H5AB,H5AC), C5B(H5BA,
 H5BB,H5BC), C6A(H6AA,H6AB,H6AC), C6B(H6BA,H6BB,H6BC), C7A(H7AA,H7AB,H7AC),
 C7B(H7BA,H7BB,H7BC), C9A(H9AA,H9AB,H9AC), C9B(H9BA,H9BB,H9BC), C10A(H10A,H10B,
 H10C), C10B(H10D,H10E,H10F), C11A(H11A,H11B,H11C), C11B(H11D,H11E,H11F),
 C12A(H12A,H12B,H12C), C12B(H12D,H12E,H12F), C13A(H13A,H13B,H13C), C13B(H13D,
 H13E,H13F), C14A(H14A,H14B,H14C), C14B(H14D,H14E,H14F), C16A(H16D,H16E,H16F),
 C16B(H16A,H16B,H16C), C17A(H17D,H17E,H17F), C17B(H17A,H17B,H17C), C18A(H18D,
 H18E,H18F), C18B(H18A,H18B,H18C), C20A(H20A,H20B,H20C), C20B(H20D,H20E,H20F),
 C21A(H21A,H21B,H21C), C21B(H21D,H21E,H21F), C22A(H22A,H22B,H22C), C22B(H22D,
 H22E,H22F)
;
_shelx_res_checksum              42671
_olex2_date_sample_data_collection 2024-06-25
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.484
_oxdiff_exptl_absorpt_empirical_full_min 0.823