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_7720118
_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         'C23 H56 Ga O3 P Si4'
_chemical_formula_sum            'C23 H56 Ga O3 P Si4'
_chemical_formula_weight         593.72
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-06-23
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2025-11-17 deposited with the CCDC.	2026-01-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 118.553(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.7399(11)
_cell_length_b                   28.1763(17)
_cell_length_c                   11.8292(9)
_cell_measurement_reflns_used    14370
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      32.2610
_cell_measurement_theta_min      3.4680
_cell_volume                     3437.0(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3114
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.903
_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    -27.00  10.00   1.00   11.00    --  -17.14 -77.00 150.00   37
  2  \w    -36.00   2.00   1.00   11.00    --  -17.14 -77.00  30.00   38
  3  \w    -76.00 -50.00   1.00   11.00    --  -17.14 -57.00 -60.00   26
  4  \w    -13.00  13.00   1.00   11.00    --   17.14 -99.00-120.00   26
  5  \w     -2.00  54.00   1.00   11.00    --   17.14 -99.00 -30.00   56
  6  \w     19.00  50.00   1.00   11.00    --   17.14 -99.00-120.00   31
  7  \w     -8.00  76.00   1.00   11.00    --   17.14  57.00-180.00   84
  8  \w     15.00  82.00   1.00   11.00    --   17.14  38.00  60.00   67
  9  \w    -54.00  38.00   1.00   11.00    --   17.14 -38.00-120.00   92
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0076402000
_diffrn_orient_matrix_UB_12      0.0238216000
_diffrn_orient_matrix_UB_13      -0.0146489000
_diffrn_orient_matrix_UB_21      -0.0623403000
_diffrn_orient_matrix_UB_22      0.0055928000
_diffrn_orient_matrix_UB_23      -0.0080067000
_diffrn_orient_matrix_UB_31      0.0280911000
_diffrn_orient_matrix_UB_32      0.0059362000
_diffrn_orient_matrix_UB_33      0.0662296000
_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  0.0347
_diffrn_reflns_av_unetI/netI     0.0336
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.903
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            49252
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.903
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.849
_diffrn_reflns_theta_min         2.892
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.006
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.448
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.90a (Rigaku Oxford Diffraction, 2023)
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    1.147
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1280
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.771
_refine_diff_density_min         -1.390
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     395
_refine_ls_number_reflns         11541
_refine_ls_number_restraints     272
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0793
_refine_ls_R_factor_gt           0.0587
_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^)+(0.0449P)^2^+6.3415P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1293
_refine_ls_wR_factor_ref         0.1413
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8998
_reflns_number_total             11541
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00151c3.cif
_cod_data_source_block           GaOPxCO2
_cod_original_cell_volume        3437.0(5)
_cod_database_code               7720118
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C23 H56 Ga O3 P Si4'
_shelx_estimated_absorpt_t_max   0.864
_shelx_estimated_absorpt_t_min   0.660
_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, All C(H,H,H,H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Si1A \\sim C2A \\sim C3A \\sim C3B: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Si2A \\sim C5A \\sim C6A \\sim C7: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Si3: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Si4A \\sim C12A \\sim C13A \\sim C14A: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C4A \\sim Si1B \\sim C2B \\sim C4B: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C7 \\sim Si2B \\sim C5B \\sim C6B: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Si4B \\sim C12B \\sim C13B \\sim C14B: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
Si3 \\sim C9A \\sim C10A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Si3 \\sim C9A \\sim C10A \\sim C11A \\sim C9B \\sim C10B \\sim C11B: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(Si1B) = Uanis(Si1A)
Uanis(C3A) = Uanis(C4B)
Uanis(C3B) = Uanis(C4A)
Uanis(C2B) = Uanis(C2A)
Uanis(Si4A) = Uanis(Si4B)
Uanis(C8B) = Uanis(C8A)
3. Rigid body (RIGU) restrains
 Si1A, C2A, C3A, C3B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C4A, Si1B, C2B, C4B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Si3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Si2A, C5A, C6A, C7
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Si4A, C12A, C13A, C14A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C7, Si2B, C5B, C6B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Si4B, C12B, C13B, C14B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Si3, C9A, C10A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Si3, C9A, C10A, C11A, C9B, C10B, C11B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Others
 Sof(H1B)=Sof(H7BD)=Sof(H7BE)=Sof(H7BF)=Sof(Si1B)=Sof(Si2B)=Sof(Si4B)=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(C8B)=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)=1-FVAR(1)
 Sof(Si1A)=Sof(Si2A)=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(H7AA)=Sof(H7AB)=Sof(H7AC)=Sof(C8A)=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)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C1(H1A), C1(H1B), C8A(H8A), C8B(H8B)
5.b Me refined with riding coordinates:
 C2A(H2AA,H2AB,H2AC), C3A(H3AA,H3AB,H3AC), C4A(H4AA,H4AB,H4AC), C5A(H5AA,H5AB,
 H5AC), C6A(H6AA,H6AB,H6AC), C7(H7AA,H7AB,H7AC), C7(H7BD,H7BE,H7BF), C9A(H9AA,
 H9AB,H9AC), C10A(H10A,H10B,H10C), C11A(H11A,H11B,H11C), C12A(H12A,H12B,H12C),
 C13A(H13A,H13B,H13C), C14A(H14A,H14B,H14C), C2B(H2BA,H2BB,H2BC), C3B(H3BA,H3BB,
 H3BC), C4B(H4BA,H4BB,H4BC), C5B(H5BA,H5BB,H5BC), C6B(H6BA,H6BB,H6BC), C9B(H9BA,
 H9BB,H9BC), C10B(H10D,H10E,H10F), C11B(H11D,H11E,H11F), C12B(H12D,H12E,H12F),
 C13B(H13D,H13E,H13F), C14B(H14D,H14E,H14F)
5.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C20(H20A,H20B,
 H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C)
;
_shelx_res_checksum              32501
_olex2_date_sample_data_collection 2023-06-23
_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 1.181
_oxdiff_exptl_absorpt_empirical_full_min 0.897