Silica-supported isolated gallium sites as highly active, selective and stable propane dehydrogenation catalysts
Searles, Keith; Siddiqi, Georges; Safonova, Olga V.; Copéret, Christophe; Chem. Sci. 8 (2017) 2661–; doi:10.1039/C6SC05178B

data_1544982
_publ_section_title
;
 Silica-supported isolated gallium sites as highly active, selective and
 stable propane dehydrogenation catalysts
;
_journal_issue                   4
_journal_name_full               'Chem. Sci.'
_journal_page_first              2661
_journal_paper_doi               10.1039/C6SC05178B
_journal_volume                  8
_journal_year                    2017
_chemical_formula_moiety         'C40 H89 Ga O13 Si3'
_chemical_formula_sum            'C40 H89 Ga O13 Si3'
_chemical_formula_weight         932.10
_chemical_name_systematic        Ga[OSi(OtBu)3]3(thf)
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2016-07-20
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2016-08-18 deposited with the CCDC.
2017-01-03 downloaded from the CCDC.
;
_cell_angle_alpha                62.983(4)
_cell_angle_beta                 89.953(3)
_cell_angle_gamma                89.655(3)
_cell_formula_units_Z            8
_cell_length_a                   18.0886(5)
_cell_length_b                   25.2724(10)
_cell_length_c                   26.1157(10)
_cell_measurement_reflns_used    14810
_cell_measurement_temperature    100.0(17)
_cell_measurement_theta_max      30.7165
_cell_measurement_theta_min      2.8441
_cell_volume                     10635.5(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      100.0(17)
_diffrn_detector_area_resol_mean 16.0839
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_details
;
  1 omega  -25.00   15.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -21.6342  -99.0000   60.0000 40

  2 omega  -25.00    8.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -21.6342  -99.0000  -60.0000 33

  3 omega  -47.00   43.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       22.2592  -57.0000    0.0000 90

  4 omega    1.00   91.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       22.2592   57.0000  -90.0000 90

  5 omega  -47.00   44.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       22.2592  -57.0000  120.0000 91

  6 omega  -42.00   47.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -21.6342   57.0000  -90.0000 89

  7 omega    1.00   26.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       22.2592   57.0000  150.0000 25
;
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0046506000
_diffrn_orient_matrix_UB_12      -0.0258149000
_diffrn_orient_matrix_UB_13      0.0266066000
_diffrn_orient_matrix_UB_21      -0.0035542000
_diffrn_orient_matrix_UB_22      0.0174881000
_diffrn_orient_matrix_UB_23      0.0147796000
_diffrn_orient_matrix_UB_31      -0.0387751000
_diffrn_orient_matrix_UB_32      -0.0044980000
_diffrn_orient_matrix_UB_33      0.0017694000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0737
_diffrn_reflns_av_unetI/netI     0.1396
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            105891
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.282
_diffrn_reflns_theta_min         2.850
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.637
_exptl_absorpt_correction_T_max  0.993
_exptl_absorpt_correction_T_min  0.975
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.164
_exptl_crystal_description       block
_exptl_crystal_F_000             4048
_exptl_crystal_preparation       'Reaction of GaCl3 with NaOSi(OtBu)3'
_exptl_crystal_size_max          0.4643
_exptl_crystal_size_mid          0.2412
_exptl_crystal_size_min          0.0987
_refine_diff_density_max         0.816
_refine_diff_density_min         -0.649
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2162
_refine_ls_number_reflns         52326
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.1188
_refine_ls_R_factor_gt           0.0741
_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^)+(0.0339P)^2^+0.8737P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1174
_refine_ls_wR_factor_ref         0.1374
_reflns_Friedel_coverage         0.000
_reflns_number_gt                34903
_reflns_number_total             52326
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6sc05178b2.cif
_cod_data_source_block           ks-1-60
_cod_depositor_comments          'Adding full bibliography for 1544982.cif.'
_cod_original_cell_volume        10635.5(7)
_cod_database_code               1544982
_chemical_oxdiff_formula         'Ga1 Si3 O12 C36 H81'
_reflns_odcompleteness_completeness 99.08
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.8855(4) 0.1145(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C158) \\sim Ueq, Uanis(C160) \\sim Ueq: with sigma of 0.05 and sigma for
terminal atoms of 0.1
4.a Secondary CH2 refined with riding coordinates:
 C121(H12D,H12E), C81(H81A,H81B), C124(H12I,H12J), C83(H83A,H83B), C82(H82A,
 H82B), C3(H3A,H3B), C123(H12K,H12L), C84(H84A,H84B), C122(H12M,H12N), C1(H1A,
 H1B), C4(H4A,H4B), C43(H43A,H43B), C2(H2A,H2B), C44(H44A,H44B), C41(H41A,H41B),
  C42(H42A,H42B)
4.b Idealised Me refined as rotating group:
 C72(H72A,H72B,H72C), C67(H67A,H67B,H67C), C102(H10A,H10B,H10C), C116(H11A,
 H11B,H11C), C75(H75A,H75B,H75C), C135(H13A,H13B,H13C), C64(H64A,H64B,H64C),
 C108(H10D,H10E,H10F), C128(H12F,H12G,H12H), C132(H13D,H13E,H13F), C32(H32A,
 H32B,H32C), C94(H94A,H94B,H94C), C103(H10G,H10H,H10I), C87(H87A,H87B,H87C),
 C63(H63A,H63B,H63C), C119(H11D,H11E,H11F), C118(H11G,H11H,H11I), C8(H8A,H8B,
 H8C), C36(H36A,H36B,H36C), C76(H76A,H76B,H76C), C38(H38A,H38B,H38C), C158(H15A,
 H15B,H15C), C120(H12A,H12B,H12C), C99(H99A,H99B,H99C), C130(H13G,H13H,H13I),
 C100(H10J,H10K,H10L), C39(H39A,H39B,H39C), C60(H60A,H60B,H60C), C23(H23A,H23B,
 H23C), C68(H68A,H68B,H68C), C28(H28A,H28B,H28C), C59(H59A,H59B,H59C),
 C106(H10M,H10N,H10O), C155(H15D,H15E,H15F), C154(H15G,H15H,H15I), C115(H11J,
 H11K,H11L), C40(H40A,H40B,H40C), C52(H52A,H52B,H52C), C136(H13J,H13K,H13L),
 C58(H58A,H58B,H58C), C70(H70A,H70B,H70C), C80(H80A,H80B,H80C), C62(H62A,H62B,
 H62C), C156(H15J,H15K,H15L), C10(H10V,H10W,H10X), C92(H92A,H92B,H92C),
 C30(H30A,H30B,H30C), C7(H7A,H7B,H7C), C131(H13M,H13N,H13O), C160(H16A,H16B,
 H16C), C14(H14V,H14W,H14X), C71(H71A,H71B,H71C), C147(H14A,H14B,H14C),
 C144(H14D,H14E,H14F), C22(H22A,H22B,H22C), C91(H91A,H91B,H91C), C127(H12O,H12P,
 H12Q), C98(H98A,H98B,H98C), C142(H14G,H14H,H14I), C47(H47A,H47B,H47C),
 C50(H50A,H50B,H50C), C24(H24A,H24B,H24C), C35(H35A,H35B,H35C), C11(H11Y,H,HA),
 C151(H15M,H15N,H15O), C110(H11M,H11N,H11O), C79(H79A,H79B,H79C), C104(H10P,
 H10Q,H10R), C148(H14J,H14K,H14L), C66(H66A,H66B,H66C), C27(H27A,H27B,H27C),
 C31(H31A,H31B,H31C), C20(H20A,H20B,H20C), C16(H16D,H16E,H16F), C51(H51A,H51B,
 H51C), C19(H19A,H19B,H19C), C78(H78A,H78B,H78C), C146(H14M,H14N,H14O),
 C114(H11P,H11Q,H11R), C143(H14P,H14Q,H14R), C46(H46A,H46B,H46C), C15(H15Y,HB,
 HC), C126(H12R,H12S,H12T), C74(H74A,H74B,H74C), C90(H90A,H90B,H90C), C86(H86A,
 H86B,H86C), C96(H96A,H96B,H96C), C152(H15P,H15Q,H15R), C140(H14S,H14T,H14U),
 C112(H11S,H11T,H11U), C12(H12U,H12V,H12W), C18(H18A,H18B,H18C), C150(H15S,H15T,
 H15U), C107(H10S,H10T,H10U), C88(H88A,H88B,H88C), C48(H48A,H48B,H48C),
 C139(H13P,H13Q,H13R), C138(H13S,H13T,H13U), C159(H15V,H15W,H15X), C134(H13V,
 H13W,H13X), C111(H11V,H11W,H11X), C55(H55A,H55B,H55C), C95(H95A,H95B,H95C),
 C54(H54A,H54B,H54C), C56(H56A,H56B,H56C), C26(H26A,H26B,H26C), C34(H34A,H34B,
 H34C), C6(H6A,H6B,H6C)
;
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2015-12-07
_olex2_exptl_crystal_mounting_method 'Mounted in paratone'
_olex2_submission_special_instructions 'No special instructions were received'