Room Temperature Acceptorless Alkane Dehydrogenation from Molecular σ-Alkane Complexes.
McKay, Alasdair I.; Bukvic, Alexander J.; Tegner, Bengt E.; Burnage, Arron L.; Martı Nez-Martı Nez, Antonio J; Rees, Nicholas H.; Macgregor, Stuart A.; Weller, Andrew S.; Journal of the American Chemical Society 141 (2019) 11700–11712; doi:10.1021/jacs.9b05577

data_4127372
_publ_section_title
;
 Room Temperature Acceptorless Alkane Dehydrogenation from Molecular
 \s-Alkane Complexes.
;
_journal_issue                   29
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11700
_journal_page_last               11712
_journal_paper_doi               10.1021/jacs.9b05577
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C30 H56 P2 Rh, C32 H12 B F24'
_chemical_formula_sum            'C62 H68 B F24 P2 Rh'
_chemical_formula_weight         1444.82
_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     dual
_audit_creation_date             2019-01-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                92.3462(17)
_cell_angle_beta                 90.9972(16)
_cell_angle_gamma                96.6033(17)
_cell_formula_units_Z            2
_cell_length_a                   12.7477(3)
_cell_length_b                   13.0092(3)
_cell_length_c                   19.8574(4)
_cell_measurement_reflns_used    33643
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      76.1770
_cell_measurement_theta_min      3.9590
_cell_volume                     3267.70(13)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_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    'XT (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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -44.00  30.00   1.00    1.75    --  -41.52  37.00  90.00   74
  2  \w    -46.00 -12.00   1.00    1.75    --  -41.52  37.00  60.00   34
  3  \w    -95.00  -3.00   1.00    1.75    --  -41.52 125.00  90.00   92
  4  \w    -35.00  26.00   1.00    1.75    --  -41.52  37.00-120.00   61
  5  \w     40.00  96.00   1.00    1.75    --   41.52-125.00 -30.00   56
  6  \w     36.00  77.00   1.00    7.00    --  111.00 -30.00 -90.00   41
  7  \w     51.00  90.00   1.00    7.00    --  111.00 -61.00 -60.00   39
  8  \w     71.00 106.00   1.00    7.00    --  111.00 -94.00 -90.00   35
  9  \w     88.00 121.00   1.00    7.00    --  111.00-125.00 -90.00   33
 10  \w     78.00 105.00   1.00    7.00    --  111.00 -94.00-120.00   27
 11  \w     91.00 118.00   1.00    7.00    --  111.00-125.00-180.00   27
 12  \w     53.00  98.00   1.00    7.00    --  111.00 -94.00-180.00   45
 13  \w     44.00  83.00   1.00    7.00    --  111.00-125.00-180.00   39
 14  \w     42.00  71.00   1.00    7.00    --  111.00-125.00 -90.00   29
 15  \w     38.00  86.00   1.00    7.00    --  111.00 -77.00 -60.00   48
 16  \w    115.00 142.00   1.00    7.00    --  111.00 -77.00   0.00   27
 17  \w    141.00 167.00   1.00    7.00    --  111.00  15.00  60.00   26
 18  \w     95.00 140.00   1.00    7.00    --  111.00 125.00  30.00   45
 19  \w     95.00 150.00   1.00    7.00    --  111.00 125.00   0.00   55
 20  \w    129.00 176.00   1.00    7.00    --  111.00 125.00 -90.00   47
 21  \w    102.00 128.00   1.00    7.00    --  111.00 125.00 -90.00   26
 22  \w     68.00 115.00   1.00    7.00    --  111.00  15.00  60.00   47
 23  \w     57.00 129.00   1.00    7.00    --  111.00 -61.00 150.00   72
 24  \w     78.00 108.00   1.00    7.00    --  111.00 -94.00 120.00   30
 25  \w     73.00 121.00   1.00    7.00    --  111.00-125.00  90.00   48
 26  \w     70.00 121.00   1.00    7.00    --  111.00-125.00  60.00   51
 27  \w     58.00  99.00   1.00    7.00    --  111.00 -45.00   0.00   41
 28  \w     47.00  91.00   1.00    7.00    --  111.00 -30.00 -30.00   44
 29  \w     44.00  91.00   1.00    7.00    --  111.00 -30.00  60.00   47
 30  \w     48.00  73.00   1.00    7.00    --  111.00 -30.00 150.00   25
 31  \w     36.00  82.00   1.00    7.00    --  111.00 -30.00 120.00   46
 32  \w     31.00  64.00   1.00    7.00    --  111.00 -94.00 120.00   33
 33  \w     43.00 112.00   1.00    7.00    --  111.00-125.00 120.00   69
 34  \w     37.00  66.00   1.00    7.00    --  111.00 -77.00   0.00   29
 35  \w     31.00 109.00   1.00    7.00    --  111.00 -94.00 -60.00   78
 36  \w     41.00  90.00   1.00    7.00    --  111.00 -30.00-150.00   49
 37  \w    144.00 171.00   1.00    7.00    --  111.00   0.00-150.00   27
 38  \w     24.00 118.00   1.00    7.00    --  111.00   0.00-150.00   94
 39  \w   -111.00 -23.00   1.00    1.75    --  -41.52 -37.00 -90.00   88
 40  \w    -17.00  12.00   1.00    1.75    --   41.52 -72.00  26.00   29
 41  \w    -36.00  -7.00   1.00    1.75    --    2.00  96.00  99.17   29
 42  \w    -88.00 -15.00   1.00    1.75    --  -41.52 -57.00-180.00   73
 43  \w   -111.00 -17.00   1.00    1.75    --  -41.52 -57.00  90.00   94
 44  \w      7.00  32.00   1.00    1.75    --   41.52  86.00  -4.30   25
 45  \w     14.00  40.00   1.00    1.75    --   46.00  81.00 158.00   26
 46  \w     17.00  42.00   1.00    1.75    --   50.00  82.00  66.63   25
 47  \w     18.00  43.00   1.00    1.75    --   50.00  80.00-108.63   25
 48  \w     18.00  43.00   1.00    1.75    --   50.00  81.00  10.10   25
 49  \w     22.00  47.00   1.00    1.75    --   54.00  78.00 -71.38   25
 50  \w     22.00  47.00   1.00    1.75    --   54.00  78.00-167.42   25
 51  \w     36.00  87.00   1.00    1.75    --   66.00  77.00 -12.54   51
 52  \w     92.00 140.00   1.00    1.75    --   66.00  77.00  77.76   48
 53  \w     35.00  86.00   1.00    1.75    --   66.00  77.00  77.76   51
 54  \w     35.00  69.00   1.00    1.75    --   66.00  77.00  45.61   34
 55  \w     35.00  69.00   1.00    1.75    --   66.00  76.00-144.64   34
 56  \w     72.00 132.00   1.00    1.75    --   66.00  77.00  45.61   60
 57  \w     35.00  66.00   1.00    1.75    --   66.00  77.00 139.40   31
 58  \w     39.00  65.00   1.00    1.75    --   70.00  77.00 -80.22   26
 59  \w     39.00  68.00   1.00    1.75    --   70.00  75.00 -51.03   29
 60  \w     40.00  65.00   1.00    1.75    --   70.00  76.00-110.06   25
 61  \w     39.00  71.00   1.00    1.75    --   70.00  76.00  21.65   32
 62  \w    123.00 148.00   1.00    1.75    --   74.00  77.00  90.47   25
 63  \w     43.00  83.00   1.00    1.75    --   74.00  77.00  90.47   40
 64  \w     46.00  86.00   1.00    1.75    --   74.00  68.00 177.66   40
 65  \w     72.00 105.00   1.00    7.00    --  102.00  70.00 -46.37   33
 66  \w     83.00 136.00   1.00    7.00    --  111.00  61.00  90.00   53
 67  \w     84.00 115.00   1.00    7.00    --  111.00  61.00  60.00   31
 68  \w     83.00 137.00   1.00    7.00    --  111.00  61.00-180.00   54
 69  \w     80.00 109.00   1.00    7.00    --  111.00  77.00-150.00   29
 70  \w    128.00 172.00   1.00    7.00    --  111.00  61.00 150.00   44
 71  \w     83.00 164.00   1.00    7.00    --  111.00  61.00-150.00   81
 72  \w     83.00 124.00   1.00    7.00    --  111.00  61.00 150.00   41
 73  \w     80.00 121.00   1.00    7.00    --  111.00  77.00  30.00   41
 74  \w     84.00 131.00   1.00    7.00    --  111.00  61.00 120.00   47
 75  \w     80.00 106.00   1.00    7.00    --  111.00  77.00 -30.00   26
 76  \w     84.00 118.00   1.00    7.00    --  111.00  59.00  74.95   34
 77  \w     83.00 147.00   1.00    7.00    --  111.00  61.00 -90.00   64
 78  \w     83.00 162.00   1.00    7.00    --  111.00  61.00-120.00   79
 79  \w     80.00 151.00   1.00    7.00    --  111.00  77.00 -90.00   71
 80  \w     83.00 157.00   1.00    7.00    --  111.00  61.00 -60.00   74
 81  \w    132.00 159.00   1.00    7.00    --  111.00  61.00   0.00   27
 82  \w     83.00 136.00   1.00    7.00    --  111.00  61.00  30.00   53
 83  \w     84.00 111.00   1.00    7.00    --  111.00  61.00   0.00   27
 84  \w     80.00 107.00   1.00    7.00    --  111.00  77.00 120.00   27
 85  \w     81.00 112.00   1.00    7.00    --  111.00  72.00 156.00   31
 86  \w     80.00 107.00   1.00    7.00    --  111.00  77.00-180.00   27
 87  \w     80.00 106.00   1.00    7.00    --  111.00  77.00  90.00   26
 88  \w    128.00 153.00   1.00    7.00    --  111.00  77.00-120.00   25
 89  \w     84.00 150.00   1.00    7.00    --  111.00  61.00 -30.00   66
 90  \w     80.00 117.00   1.00    7.00    --  111.00  77.00-120.00   37
 91  \w     80.00 131.00   1.00    7.00    --  111.00  77.00   0.00   51
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1205865000
_diffrn_orient_matrix_UB_12      -0.0017825000
_diffrn_orient_matrix_UB_13      -0.0010977000
_diffrn_orient_matrix_UB_21      -0.0057353000
_diffrn_orient_matrix_UB_22      -0.0663423000
_diffrn_orient_matrix_UB_23      0.0626274000
_diffrn_orient_matrix_UB_31      -0.0152898000
_diffrn_orient_matrix_UB_32      -0.0991644000
_diffrn_orient_matrix_UB_33      -0.0459190000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0406
_diffrn_reflns_av_unetI/netI     0.0226
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            77320
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.075
_diffrn_reflns_theta_min         3.491
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.530
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66113
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43b (Rigaku Oxford Diffraction, 2015)
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    1.468
_exptl_crystal_description       block
_exptl_crystal_F_000             1472
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.16
_refine_diff_density_max         2.376
_refine_diff_density_min         -1.122
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1014
_refine_ls_number_reflns         12411
_refine_ls_number_restraints     791
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0553
_refine_ls_R_factor_gt           0.0511
_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^)+(0.0695P)^2^+6.7545P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1475
_refine_ls_wR_factor_ref         0.1509
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11368
_reflns_number_total             12411
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b05577_si_002.cif
_cod_data_source_block           1-C4H8
_cod_original_cell_volume        3267.71(12)
_cod_database_code               4127372
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C54 H66 Rh1 P2 F24 B1'
_shelx_estimated_absorpt_t_max   0.602
_shelx_estimated_absorpt_t_min   0.461
_reflns_odcompleteness_completeness 99.93
_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
 F11-F10 \\sim F11-F12 \\sim F10-F12 \\sim F12A-F10A \\sim F12A-F11A \\sim
F10A-F11A
 with sigma of 0.04
 C46-F11 \\sim C46-F10 \\sim C46-F12 \\sim C46-F12A \\sim C46-F10A \\sim
C46-F11A
 with sigma of 0.02
 F22-F23 \\sim F23-F24 \\sim F24A-F23A \\sim F24A-F22A
 with sigma of 0.04
 C62-F22 \\sim C62-F23 \\sim C62-F24 \\sim C62-F24A \\sim C62-F23A \\sim
C62-F22A
 with sigma of 0.02
 F17-F16 \\sim F16A-F18A
 with sigma of 0.04
 C54-F17 \\sim C54-F18 \\sim C54-F16 \\sim C54-F16A \\sim C54-F18A \\sim
C54-F17A
 with sigma of 0.02
 F13-F14 \\sim F14-F15 \\sim F14A-F15A \\sim F14A-F13A \\sim F15A-F13A
 with sigma of 0.04
 C53-F13 \\sim C53-F14 \\sim C53-F15 \\sim C53-F14A \\sim C53-F15A \\sim
C53-F13A
 with sigma of 0.02
 F1-F2 \\sim F1-F3 \\sim F3A-F2A \\sim F3A-F1A \\sim F2A-F1A \\sim F2-F3
 with sigma of 0.04
 C37-F1 \\sim C37-F3A \\sim C37-F2A \\sim C37-F2 \\sim C37-F3 \\sim C37-F1A
 with sigma of 0.02
 F9-F8 \\sim F9-F7 \\sim F8-F7 \\sim F7A-F8A \\sim F7A-F9A \\sim F8A-F9A
 with sigma of 0.04
 C45-F9 \\sim C45-F8 \\sim C45-F7 \\sim C45-F7A \\sim C45-F8A \\sim C45-F9A
 with sigma of 0.02
 C4A-C2A \\sim C4-C2
 with sigma of 0.02
 C1A-C2A \\sim C1-C2
 with sigma of 0.02
 C3-C2 \\sim C3A-C2A
 with sigma of 0.02
3. Rigid bond restraints
 F1, F2, F3, F1A, F2A, F3A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C46 \\sim F10 \\sim F11 \\sim F12 \\sim F10A \\sim F11A \\sim F12A: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
C62 \\sim F22 \\sim F23 \\sim F24 \\sim F22A \\sim F23A \\sim F24A: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
C54 \\sim F16 \\sim F17 \\sim F18 \\sim F16A \\sim F17A \\sim F18A: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
C53 \\sim F13 \\sim F14 \\sim F15 \\sim F13A \\sim F14A \\sim F15A: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
C37 \\sim F1 \\sim F2 \\sim F3 \\sim F1A \\sim F2A \\sim F3A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C45 \\sim F7 \\sim F8 \\sim F9 \\sim F7A \\sim F8A \\sim F9A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C4) = Uanis(C4A)
5. Rigid body (RIGU) restrains
 C46, F10, F11, F12, F10A, F11A, F12A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C62, F22, F23, F24, F22A, F23A, F24A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C54, F16, F17, F18, F16A, F17A, F18A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C53, F13, F14, F15, F13A, F14A, F15A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C37, F1, F2, F3, F1A, F2A, F3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C45, F7, F8, F9, F7A, F8A, F9A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(C2A)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=
 Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=1-FVAR(1)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C4)=
 Sof(H4A)=Sof(H4B)=Sof(H4C)=FVAR(1)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(2)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(2)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(3)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(3)
 Sof(F22A)=Sof(F23A)=Sof(F24A)=1-FVAR(4)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(4)
 Sof(F16A)=Sof(F17A)=Sof(F18A)=1-FVAR(5)
 Sof(F16)=Sof(F17)=Sof(F18)=FVAR(5)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=1-FVAR(6)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(6)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(7)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(7)
7.a Ternary CH refined with riding coordinates:
 C7(H7), C13(H13), C19(H19), C25(H25)
7.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,
 H11B), C12(H12A,H12B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B),
 C17(H17A,H17B), C18(H18A,H18B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B),
  C23(H23A,H23B), C24(H24A,H24B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,
 H28B), C29(H29A,H29B), C30(H30A,H30B)
7.c Aromatic/amide H refined with riding coordinates:
 C32(H32), C34(H34), C36(H36), C40(H40), C42(H42), C44(H44), C48(H48),
 C50(H50), C52(H52), C56(H56), C58(H58), C60(H60)
7.d X=CH2 refined with riding coordinates:
 C1(H1A,H1B), C1A(H1AA,H1AB)
7.e Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C3A(H3AA,H3AB,H3AC), C4A(H4AA,H4AB,H4AC)
;
_shelx_res_checksum              47564
_shelx_hkl_checksum              70723
_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 1.961
_oxdiff_exptl_absorpt_empirical_full_min 0.680