Solid–State Molecular Organometallic Catalysis in Gas/Solid Flow (Flow-SMOM) as Demonstrated by Efficient Room Temperature and Pressure 1-Butene Isomerization
Martínez-Martínez, Antonio J.; Royle, Cameron G.; Furfari, Samantha K.; Suriye, Kongkiat; Weller, Andrew S.; ACS Catalysis  (2020) 1984–1992; doi:10.1021/acscatal.9b03727

data_4517328
_publ_section_title
;
 Solid--State Molecular Organometallic Catalysis in Gas/Solid Flow
 (Flow-SMOM) as Demonstrated by Efficient Room Temperature and Pressure
 1-Butene Isomerization
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              1984
_journal_page_last               1992
_journal_paper_doi               10.1021/acscatal.9b03727
_journal_year                    2020
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C25 H48 P2 Rh, C32 H12 B F24'
_chemical_formula_sum            'C57 H60 B F24 P2 Rh'
_chemical_formula_weight         1376.71
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.1029(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.1357(3)
_cell_length_b                   18.1424(4)
_cell_length_c                   17.9779(4)
_cell_measurement_reflns_used    30877
_cell_measurement_temperature    150.01(12)
_cell_measurement_theta_max      76.1780
_cell_measurement_theta_min      4.1910
_cell_volume                     5915.2(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.31c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.31c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.31c (Rigaku OD, 2017)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(12)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4102
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_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    -35.00  14.00   1.00    1.00    --  -42.66  38.00-150.00   49
  2  \w   -107.00 -20.00   1.00    1.00    --  -42.66 -77.00 -90.00   87
  3  \w     88.00 125.00   1.00    1.00    --   42.66 178.00 -30.00   37
  4  \w     69.00  97.00   1.00    4.00    --  111.00 -45.00  90.00   28
  5  \w     51.00  97.00   1.00    4.00    --  111.00 -95.00 -30.00   46
  6  \w     50.00  89.00   1.00    4.00    --  111.00 -30.00  60.00   39
  7  \w     38.00  86.00   1.00    4.00    --  111.00 -30.00-120.00   48
  8  \w     62.00  87.00   1.00    4.00    --  111.00 -30.00 -30.00   25
  9  \w     90.00 156.00   1.00    4.00    --  111.00  45.00-150.00   66
 10  \w     46.00 102.00   1.00    4.00    --  111.00-106.00 -82.00   56
 11  \w     45.00 112.00   1.00    4.00    --  111.00-125.00 120.00   67
 12  \w    -25.00  16.00   1.00    1.00    --  -42.66  38.00  60.00   41
 13  \w     63.00 116.00   1.00    1.00    --   42.66 178.00-150.00   53
 14  \w     70.00  96.00   1.00    4.00    --  111.00 -77.00 -90.00   26
 15  \w     36.00  87.00   1.00    4.00    --  111.00 -30.00 120.00   51
 16  \w     66.00  92.00   1.00    4.00    --  111.00 -45.00 -60.00   26
 17  \w    114.00 142.00   1.00    4.00    --  111.00 -77.00 -90.00   28
 18  \w     43.00  91.00   1.00    4.00    --  111.00 -30.00 -60.00   48
 19  \w    152.00 178.00   1.00    4.00    --  111.00 125.00 -30.00   26
 20  \w    126.00 167.00   1.00    4.00    --  111.00  45.00-120.00   41
 21  \w     65.00  91.00   1.00    4.00    --  111.00 -45.00 -90.00   26
 22  \w     76.00 109.00   1.00    4.00    --  111.00  15.00  30.00   33
 23  \w    -38.00   1.00   1.00    1.00    --  -42.66  38.00   0.00   39
 24  \w     99.00 126.00   1.00    1.00    --   42.66 178.00 -30.00   27
 25  \w     68.00  94.00   1.00    4.00    --  111.00-125.00 -30.00   26
 26  \w    140.00 175.00   1.00    4.00    --  111.00  30.00 -30.00   35
 27  \w     93.00 118.00   1.00    4.00    --  111.00-125.00 -90.00   25
 28  \w     86.00 135.00   1.00    4.00    --  111.00 -61.00  90.00   49
 29  \w     59.00 118.00   1.00    4.00    --  111.00-125.00-180.00   59
 30  \w    121.00 147.00   1.00    4.00    --  111.00  45.00   0.00   26
 31  \w    -46.00   8.00   1.00    1.00    --  -42.66  38.00-180.00   54
 32  \w    -45.00  -4.00   1.00    1.00    --  -42.66  38.00 -30.00   41
 33  \w    -49.00  25.00   1.00    1.00    --  -42.66  38.00 -90.00   74
 34  \w     99.00 126.00   1.00    1.00    --   42.66 178.00   0.00   27
 35  \w     94.00 157.00   1.00    4.00    --  111.00  61.00  30.00   63
 36  \w     77.00 118.00   1.00    4.00    --  111.00-125.00  60.00   41
 37  \w     90.00 117.00   1.00    4.00    --  111.00-125.00-120.00   27
 38  \w     43.00  84.00   1.00    4.00    --  111.00 -15.00  60.00   41
 39  \w     46.00 108.00   1.00    4.00    --  111.00 -61.00  30.00   62
 40  \w    111.00 148.00   1.00    4.00    --  111.00 -15.00  60.00   37
 41  \w     55.00  89.00   1.00    4.00    --  111.00 -45.00-150.00   34
 42  \w     30.00  81.00   1.00    4.00    --  111.00 -95.00-120.00   51
 43  \w     78.00 118.00   1.00    4.00    --  111.00-125.00  30.00   40
 44  \w     91.00 117.00   1.00    4.00    --  111.00-125.00 150.00   26
 45  \w     94.00 139.00   1.00    4.00    --  111.00  30.00  30.00   45
 46  \w     86.00 112.00   1.00    4.00    --  111.00-125.00  90.00   26
 47  \w     50.00  76.00   1.00    4.00    --  111.00 -45.00 120.00   26
 48  \w     44.00  73.00   1.00    4.00    --  111.00 -30.00-180.00   29
 49  \w     65.00 129.00   1.00    4.00    --  111.00 -15.00-120.00   64
 50  \w    -10.00  22.00   1.00    1.00    --  -42.66  77.00  60.00   32
 51  \w    -71.00 -38.00   1.00    1.00    --  -42.66  77.00  60.00   33
 52  \w    -35.00  -9.00   1.00    1.00    --  -42.66  38.00  30.00   26
 53  \w     43.00  85.00   1.00    4.00    --  111.00 -30.00  30.00   42
 54  \w     94.00 120.00   1.00    4.00    --  111.00  45.00  90.00   26
 55  \w    140.00 175.00   1.00    4.00    --  111.00  45.00  90.00   35
 56  \w     53.00  79.00   1.00    4.00    --  111.00-125.00  30.00   26
 57  \w     64.00  90.00   1.00    4.00    --  111.00 -45.00  60.00   26
 58  \w     46.00  72.00   1.00    4.00    --  111.00 -45.00-120.00   26
 59  \w    112.00 148.00   1.00    4.00    --  111.00  45.00 -90.00   36
;
_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      0.0124276000
_diffrn_orient_matrix_UB_12      -0.0475792000
_diffrn_orient_matrix_UB_13      0.0698928000
_diffrn_orient_matrix_UB_21      -0.0186321000
_diffrn_orient_matrix_UB_22      -0.0697966000
_diffrn_orient_matrix_UB_23      -0.0450575000
_diffrn_orient_matrix_UB_31      0.0819407000
_diffrn_orient_matrix_UB_32      -0.0086740000
_diffrn_orient_matrix_UB_33      -0.0206865000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0330
_diffrn_reflns_av_unetI/netI     0.0275
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            43751
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.204
_diffrn_reflns_theta_min         3.446
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.869
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.41583
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.31c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.546
_exptl_crystal_description       plate
_exptl_crystal_F_000             2792
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.539
_refine_diff_density_min         -0.228
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 5681 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.0175(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     994
_refine_ls_number_reflns         12248
_refine_ls_number_restraints     1093
_refine_ls_restrained_S_all      1.113
_refine_ls_R_factor_all          0.0273
_refine_ls_R_factor_gt           0.0269
_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^)+(0.0443P)^2^+2.5718P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0706
_refine_ls_wR_factor_ref         0.0711
_reflns_Friedel_coverage         0.925
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.983
_reflns_number_gt                12088
_reflns_number_total             12248
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b03727_si_002.cif
_cod_data_source_block           7
_cod_depositor_comments
'Adding full bibliography for 4517328--4517333.cif.'
_cod_database_code               4517328
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C54 H66 Rh1 B1 P2 F24'
_shelx_estimated_absorpt_t_max   0.654
_shelx_estimated_absorpt_t_min   0.576
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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. Restrained distances
 F3-F2 \\sim F3-F1 \\sim F2-F1 \\sim F3A-F2A \\sim F3A-F1A \\sim F2A-F1A
 with sigma of 0.04
 C32-F3 \\sim C32-F2 \\sim C32-F1 \\sim C32-F3A \\sim C32-F2A \\sim C32-F1A
 with sigma of 0.02
 F6-F5 \\sim F6-F4 \\sim F5-F4 \\sim F6A-F5A \\sim F6A-F4A \\sim F5A-F4A
 with sigma of 0.04
 C33-F6 \\sim C33-F5 \\sim C33-F4 \\sim C33-F6A \\sim C33-F5A \\sim C33-F4A
 with sigma of 0.02
 F23-F22 \\sim F23-F24 \\sim F23A-F22A \\sim F23A-F24A \\sim F22A-F24A \\sim
F22-F24
 with sigma of 0.04
 C58-F23 \\sim C58-F23A \\sim C58-F22A \\sim C58-F22 \\sim C58-F24 \\sim
C58-F24A
 with sigma of 0.02
 F9-F7 \\sim F9-F8 \\sim F7-F8 \\sim F9A-F7A \\sim F9A-F8A \\sim F7A-F8A
 with sigma of 0.04
 C40-F9 \\sim C40-F7 \\sim C40-F8 \\sim C40-F9A \\sim C40-F7A \\sim C40-F8A
 with sigma of 0.02
 F12-F11 \\sim F12-F10 \\sim F11-F10 \\sim F12A-F11A \\sim F12A-F10A \\sim
F11A-F10A
 with sigma of 0.04
 C41-F12 \\sim C41-F11 \\sim C41-F10 \\sim C41-F12A \\sim C41-F11A \\sim
C41-F10A
 with sigma of 0.02
 F13-F15 \\sim F13-F14 \\sim F15-F14 \\sim F13A-F15A \\sim F13A-F14A \\sim
F15A-F14A
 with sigma of 0.04
 C48-F13 \\sim C48-F15 \\sim C48-F14 \\sim C48-F13A \\sim C48-F15A \\sim
C48-F14A
 with sigma of 0.02
 F17-F18 \\sim F17-F16 \\sim F18-F16 \\sim F17A-F18A \\sim F17A-F16A \\sim
F18A-F16A
 with sigma of 0.04
 C49-F17 \\sim C49-F18 \\sim C49-F16 \\sim C49-F17A \\sim C49-F18A \\sim
C49-F16A
 with sigma of 0.02
 F20-F21 \\sim F20-F19 \\sim F21-F19 \\sim F21A-F19A \\sim F21A-F20A \\sim
F19A-F20A
 with sigma of 0.04
 C57-F20 \\sim C57-F21 \\sim C57-F19 \\sim C57-F21A \\sim C57-F19A \\sim
C57-F20A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F3 \\sim F2 \\sim F1 \\sim C32 \\sim F3A \\sim F2A \\sim F1A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01
F6 \\sim F5 \\sim F4 \\sim C33 \\sim F6A \\sim F5A \\sim F4A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01
F24 \\sim F22 \\sim F23 \\sim C58 \\sim F24A \\sim F22A \\sim F23A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
F9 \\sim F7 \\sim F8 \\sim C40 \\sim F9A \\sim F7A \\sim F8A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01
F12 \\sim F11 \\sim F10 \\sim C41 \\sim F12A \\sim F11A \\sim F10A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
F13 \\sim F15 \\sim F14 \\sim C48 \\sim F13A \\sim F15A \\sim F14A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
F17 \\sim F18 \\sim F16 \\sim C49 \\sim F17A \\sim F18A \\sim F16A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
F20 \\sim F21 \\sim F19 \\sim C57 \\sim F21A \\sim F19A \\sim F20A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 F3, F2, F1, C32, F3A, F2A, F1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F6, F5, F4, C33, F6A, F5A, F4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F24, F22, F23, C58, F24A, F22A, F23A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F9, F7, F8, C40, F9A, F7A, F8A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F12, F11, F10, C41, F12A, F11A, F10A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F13, F15, F14, C48, F13A, F15A, F14A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F17, F18, F16, C49, F17A, F18A, F16A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F20, F21, F19, C57, F21A, F19A, F20A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: F12(0.61835) F20(0.62802) F11(0.61835) F3(0.69571) F6(0.56251)
 F9(0.46273) F2(0.69571) F17(0.94019) F18(0.94019) F10(0.61835) F21(0.62802)
 F24(0.69638) F13(0.71946) F15(0.71946) F19(0.62802) F16(0.94019) F1(0.69571)
 F22(0.69638) F23(0.69638) F7(0.46273) F14(0.71946) F8(0.46273) F5(0.56251)
 F4(0.56251) F3A(0.30429) F2A(0.30429) F1A(0.30429) F6A(0.43749) F5A(0.43749)
 F4A(0.43749) F24A(0.30362) F22A(0.30362) F23A(0.30362) F9A(0.53727)
 F7A(0.53727) F8A(0.53727) F12A(0.38165) F11A(0.38165) F10A(0.38165)
 F13A(0.28054) F15A(0.28054) F14A(0.28054) F17A(0.05981) F18A(0.05981)
 F16A(0.05981) F21A(0.37198) F19A(0.37198) F20A(0.37198)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C4(H4), C2(H2), C5(H5), C6(H6), C3(H3)
6.b Secondary CH2 refined with riding coordinates:
 C7(H7a,H7b), C8(H8a,H8b), C9(H9a,H9b)
6.c Aromatic/amide H refined with riding coordinates:
 C47(H47), C51(H51), C27(H27), C29(H29), C31(H31), C35(H35), C39(H39),
 C37(H37), C53(H53), C55(H55), C45(H45), C43(H43)
6.d Idealised Me refined as rotating group:
 C21(H21a,H21b,H21c), C12(H12a,H12b,H12c), C15(H15a,H15b,H15c), C25(H25a,H25b,
 H25c), C13(H13a,H13b,H13c), C11(H11a,H11b,H11c), C19(H19a,H19b,H19c), C24(H24a,
 H24b,H24c), C23(H23a,H23b,H23c), C20(H20a,H20b,H20c), C16(H16a,H16b,H16c),
 C17(H17a,H17b,H17c)
;
_shelx_res_checksum              40934
_shelx_hkl_checksum              5173
_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 1.556
_oxdiff_exptl_absorpt_empirical_full_min 0.655