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_4517330
_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_formula_moiety         'C22 H48 P2 Rh, C32 H12 B F24'
_chemical_formula_sum            'C54 H60 B F24 P2 Rh'
_chemical_formula_weight         1340.68
_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             2019-01-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.4570(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.8945(2)
_cell_length_b                   17.8193(2)
_cell_length_c                   23.5243(4)
_cell_measurement_reflns_used    16137
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      76.4280
_cell_measurement_theta_min      3.1120
_cell_volume                     5787.44(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5035
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_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    -72.00 -36.00   1.00    4.00    --    0.00-178.00   0.00   36
  2  \w     10.00  42.00   1.00    4.00    --    0.00 -99.00 -30.00   32
  3  \w     17.00  44.00   1.00    4.00    --    0.00 -99.00   0.00   27
  4  \w      3.00  43.00   1.00    4.00    --    0.00 -99.00 -90.00   40
  5  \w    -47.00  17.00   1.00   12.00    --  -60.50  30.00 150.00   64
  6  \w    -47.00  30.00   1.00   12.00    --  -60.50  30.00 -30.00   77
  7  \w    -11.00  30.00   1.00   12.00    --  -60.50  30.00-180.00   41
  8  \w    106.00 131.00   1.00   12.00    --   60.50 125.00 -90.00   25
  9  \w    119.00 152.00   1.00   12.00    --   60.50 125.00  60.00   33
 10  \w     97.00 152.00   1.00   12.00    --   60.50 125.00   0.00   55
 11  \w     44.00 103.00   1.00   12.00    --   60.50 -94.00  90.00   59
 12  \w    115.00 144.00   1.00   12.00    --   60.50 125.00-180.00   29
 13  \w     -4.00  22.00   1.00   12.00    --   60.50 -94.00  90.00   26
 14  \w     85.00 164.00   1.00   22.00    --  121.00 -77.00 150.00   79
 15  \w    118.00 177.00   1.00   22.00    --  121.00 111.00-120.00   59
 16  \w     24.00  50.00   1.00   22.00    --  121.00 -77.00 150.00   26
 17  \w    132.00 178.00   1.00   22.00    --  121.00  37.00  30.00   46
 18  \w    140.00 165.00   1.00   22.00    --  121.00 111.00 -90.00   25
 19  \w    103.00 165.00   1.00   22.00    --  121.00 -77.00-180.00   62
 20  \w    141.00 175.00   1.00   22.00    --  121.00  37.00 -60.00   34
 21  \w     21.00  86.00   1.00   22.00    --  121.00 -77.00-180.00   65
 22  \w    100.00 126.00   1.00   22.00    --  121.00  37.00  30.00   26
 23  \w     74.00 135.00   1.00   22.00    --  121.00  37.00 -60.00   61
 24  \w    130.00 177.00   1.00   22.00    --  121.00  50.00-120.00   47
 25  \w     79.00 107.00   1.00   22.00    --  121.00  50.00-120.00   28
 26  \w    132.00 170.00   1.00   22.00    --  121.00 111.00   0.00   38
 27  \w    101.00 136.00   1.00   22.00    --  121.00 111.00 -90.00   35
 28  \w    114.00 163.00   1.00   22.00    --  121.00 -63.00 -60.00   49
 29  \w    -78.00 -35.00   1.00    4.00    --    0.00-178.00 -60.00   43
 30  \w    -97.00 -70.00   1.00    4.00    --    0.00 178.00-120.00   27
 31  \w     21.00  48.00   1.00    4.00    --    0.00 -99.00 -60.00   27
 32  \w      1.00  51.00   1.00    4.00    --    0.00 -99.00  90.00   50
 33  \w   -121.00 -83.00   1.00   12.00    --  -60.50 -94.00-150.00   38
 34  \w   -155.00 -39.00   1.00   12.00    --  -60.50 -15.00  30.00  116
 35  \w    127.00 152.00   1.00   12.00    --   60.50 125.00-180.00   25
 36  \w     28.00  59.00   1.00   12.00    --   60.50-125.00-120.00   31
 37  \w     86.00 117.00   1.00   12.00    --   60.50-125.00-120.00   31
 38  \w    106.00 151.00   1.00   12.00    --   60.50 125.00 120.00   45
 39  \w     40.00 105.00   1.00   22.00    --  121.00-111.00  90.00   65
 40  \w     39.00  65.00   1.00   22.00    --  121.00-111.00 -30.00   26
 41  \w     83.00 112.00   1.00   22.00    --  121.00-111.00 -30.00   29
 42  \w    151.00 177.00   1.00   22.00    --  121.00  55.00  69.00   26
 43  \w     52.00  89.00   1.00   22.00    --  121.00-111.00 120.00   37
 44  \w     93.00 178.00   1.00   22.00    --  121.00  50.00  60.00   85
 45  \w    128.00 172.00   1.00   22.00    --  121.00  50.00   0.00   44
 46  \w    143.00 169.00   1.00   22.00    --  121.00  92.00 -64.00   26
 47  \w     76.00 102.00   1.00   22.00    --  121.00-111.00 -60.00   26
 48  \w    148.00 174.00   1.00   22.00    --  121.00  63.00  30.00   26
 49  \w     93.00 122.00   1.00   22.00    --  121.00  63.00  30.00   29
 50  \w     67.00 110.00   1.00   22.00    --  121.00-111.00-180.00   43
 51  \w     85.00 111.00   1.00   22.00    --  121.00 178.00  90.00   26
 52  \w    113.00 143.00   1.00   22.00    --  121.00 178.00  90.00   30
 53  \w     30.00  63.00   1.00   22.00    --  121.00 -50.00-180.00   33
 54  \w     67.00  93.00   1.00   22.00    --  121.00 -50.00-180.00   26
 55  \w    146.00 172.00   1.00   22.00    --  121.00  77.00-120.00   26
 56  \w    116.00 142.00   1.00   22.00    --  121.00  55.00  69.00   26
 57  \w    118.00 175.00   1.00   22.00    --  121.00  50.00 -30.00   57
 58  \w     80.00 112.00   1.00   22.00    --  121.00  50.00 -30.00   32
 59  \w     77.00 103.00   1.00   22.00    --  121.00  77.00-120.00   26
 60  \w     32.00  57.00   1.00   22.00    --  121.00-111.00 -60.00   25
 61  \w     84.00 111.00   1.00   22.00    --  121.00-111.00-150.00   27
 62  \w     86.00 112.00   1.00   22.00    --  121.00-111.00 -90.00   26
;
_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      0.0562576000
_diffrn_orient_matrix_UB_12      0.0409119000
_diffrn_orient_matrix_UB_13      -0.0435822000
_diffrn_orient_matrix_UB_21      -0.0676598000
_diffrn_orient_matrix_UB_22      0.0682994000
_diffrn_orient_matrix_UB_23      0.0016319000
_diffrn_orient_matrix_UB_31      0.0685909000
_diffrn_orient_matrix_UB_32      0.0337690000
_diffrn_orient_matrix_UB_33      0.0493963000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0531
_diffrn_reflns_av_unetI/netI     0.0406
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            55357
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.684
_diffrn_reflns_theta_min         3.118
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.936
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69245
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.539
_exptl_crystal_description       plate
_exptl_crystal_F_000             2720
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.738
_refine_diff_density_min         -1.021
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     988
_refine_ls_number_reflns         12140
_refine_ls_number_restraints     961
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.0550
_refine_ls_R_factor_gt           0.0410
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0565P)^2^+2.4953P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1040
_refine_ls_wR_factor_ref         0.1133
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9711
_reflns_number_total             12140
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b03727_si_002.cif
_cod_data_source_block           10_and_11
_cod_depositor_comments
'Adding full bibliography for 4517328--4517333.cif.'
_cod_database_code               4517330
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C54 H66 Rh1 P2 B1 F24'
_shelx_estimated_absorpt_t_max   0.798
_shelx_estimated_absorpt_t_min   0.538
_reflns_odcompleteness_completeness 99.97
_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
 F14A-F15A \\sim F14A-F13A \\sim F14-F15 \\sim F14-F13 \\sim F15A-F13A \\sim
F15-F13
 with sigma of 0.04
 C45-F14A \\sim C45-F14 \\sim C45-F15A \\sim C45-F15 \\sim C45-F13 \\sim
C45-F13A
 with sigma of 0.02
 F17-F18 \\sim F17-F16 \\sim F17A-F18A \\sim F17A-F16A \\sim F18-F16 \\sim
F18A-F16A
 with sigma of 0.04
 C46-F17 \\sim C46-F17A \\sim C46-F18 \\sim C46-F18A \\sim C46-F16 \\sim
C46-F16A
 with sigma of 0.02
 F5-F4 \\sim F5-F6 \\sim F5A-F4A \\sim F5A-F6A \\sim F4-F6 \\sim F4A-F6A
 with sigma of 0.04
 C30-F5 \\sim C30-F5A \\sim C30-F4 \\sim C30-F4A \\sim C30-F6 \\sim C30-F6A
 with sigma of 0.02
 F3A-F2A \\sim F3A-F1A \\sim F3-F2 \\sim F3-F1 \\sim F2-F1 \\sim F2A-F1A
 with sigma of 0.04
 C29-F3A \\sim C29-F3 \\sim C29-F2 \\sim C29-F2A \\sim C29-F1A \\sim C29-F1
 with sigma of 0.02
 F24A-F23A \\sim F24A-F22A \\sim F24-F23 \\sim F24-F22 \\sim F23A-F22A \\sim
F23-F22
 with sigma of 0.04
 C54-F24A \\sim C54-F24 \\sim C54-F23A \\sim C54-F23 \\sim C54-F22 \\sim
C54-F22A
 with sigma of 0.02
 F8A-F9A \\sim F8A-F7A \\sim F8-F9 \\sim F8-F7 \\sim F9-F7 \\sim F9A-F7A
 with sigma of 0.04
 C37-F8A \\sim C37-F8 \\sim C37-F9 \\sim C37-F9A \\sim C37-F7A \\sim C37-F7
 with sigma of 0.02
 F11-F12 \\sim F11-F10 \\sim F11A-F12A \\sim F11A-F10A \\sim F12-F10 \\sim
F12A-F10A
 with sigma of 0.04
 C38-F11 \\sim C38-F11A \\sim C38-F12 \\sim C38-F12A \\sim C38-F10 \\sim
C38-F10A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F13 \\sim F15 \\sim F14 \\sim C45 \\sim F13A \\sim F15A \\sim F14A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
F18 \\sim F16 \\sim F17 \\sim C46 \\sim F18A \\sim F16A \\sim F17A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
F6 \\sim F5 \\sim C30 \\sim F4 \\sim F6A \\sim F5A \\sim F4A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
F2 \\sim F1 \\sim F3 \\sim C29 \\sim F2A \\sim F1A \\sim F3A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01
F22 \\sim F24 \\sim F23 \\sim C54 \\sim F22A \\sim F24A \\sim F23A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
F7 \\sim F9 \\sim F8 \\sim C37 \\sim F7A \\sim F9A \\sim F8A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01
F12 \\sim F11 \\sim F10 \\sim C38 \\sim F12A \\sim F11A \\sim F10A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 F13, F15, F14, C45, F13A, F15A, F14A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F18, F16, F17, C46, F18A, F16A, F17A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F6, F5, C30, F4, F6A, F5A, F4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F2, F1, F3, C29, F2A, F1A, F3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F22, F24, F23, C54, F22A, F24A, F23A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F7, F9, F8, C37, F7A, F9A, F8A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F12, F11, F10, C38, F12A, F11A, F10A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 1*[Sof(C4)+Sof(H4A)+Sof(H4B)+Sof(H4C)+Sof(C1)+Sof(H1A)+Sof(H1B)+Sof(H1C)+
 Sof(C3)+Sof(H3)+Sof(C2)+Sof(H2)]+1*[Sof(C2A)+Sof(H2A)+Sof(C3A)+Sof(H3AA)+
 Sof(H3AB)+Sof(C1A)+Sof(H1AA)+Sof(H1AB)+Sof(C4A)+Sof(H4AA)+Sof(H4AB)+Sof(H4AC)]=
 1 with esd of 0.0001
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C3)=
 Sof(H3)=Sof(C2)=Sof(H2)=FVAR(1)
 Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=
 Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=FVAR(2)
 Sof(F13A)=Sof(F15A)=Sof(F14A)=1-FVAR(3)
 Sof(F13)=Sof(F15)=Sof(F14)=FVAR(3)
 Sof(F18A)=Sof(F16A)=Sof(F17A)=1-FVAR(4)
 Sof(F18)=Sof(F16)=Sof(F17)=FVAR(4)
 Sof(F6A)=Sof(F5A)=Sof(F4A)=1-FVAR(5)
 Sof(F6)=Sof(F5)=Sof(F4)=FVAR(5)
 Sof(F2A)=Sof(F1A)=Sof(F3A)=1-FVAR(6)
 Sof(F2)=Sof(F1)=Sof(F3)=FVAR(6)
 Sof(F22A)=Sof(F24A)=Sof(F23A)=1-FVAR(7)
 Sof(F22)=Sof(F24)=Sof(F23)=FVAR(7)
 Sof(F7A)=Sof(F9A)=Sof(F8A)=1-FVAR(8)
 Sof(F7)=Sof(F9)=Sof(F8)=FVAR(8)
 Sof(F12A)=Sof(F11A)=Sof(F10A)=1-FVAR(9)
 Sof(F12)=Sof(F11)=Sof(F10)=FVAR(9)
6.a Ternary CH refined with riding coordinates:
 C3(H3), C2(H2)
6.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C3A(H3AA,H3AB)
6.c Aromatic/amide H refined with riding coordinates:
 C40(H40), C28(H28), C44(H44), C24(H24), C48(H48), C42(H42), C32(H32),
 C36(H36), C26(H26), C52(H52), C34(H34), C50(H50), C2A(H2A)
6.d X=CH2 refined with riding coordinates:
 C1A(H1AA,H1AB)
6.e Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C10(H10A,H10B,H10C), C22(H22A,H22B,H22C), C16(H16A,H16B,
 H16C), C14(H14A,H14B,H14C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C9(H9A,
 H9B,H9C), C13(H13A,H13B,H13C), C21(H21A,H21B,H21C), C12(H12A,H12B,H12C),
 C8(H8A,H8B,H8C), C4(H4A,H4B,H4C), C1(H1A,H1B,H1C), C4A(H4AA,H4AB,H4AC)
;
_shelx_res_checksum              42027
_shelx_hkl_checksum              33414
_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 1.882
_oxdiff_exptl_absorpt_empirical_full_min 0.409