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_4127374
_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             2019-01-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                92.028(6)
_cell_angle_beta                 90.685(7)
_cell_angle_gamma                96.2300(10)
_cell_formula_units_Z            2
_cell_length_a                   12.7582(16)
_cell_length_b                   12.9595(15)
_cell_length_c                   19.8097(8)
_cell_measurement_reflns_used    3254
_cell_measurement_temperature    150.01(11)
_cell_measurement_theta_max      74.0390
_cell_measurement_theta_min      3.4400
_cell_volume                     3253.5(6)
_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(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4102
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.857
_diffrn_measured_fraction_theta_max 0.857
_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      2.00  28.00   1.00    3.00    --  -42.16  57.00-180.00   26
  2  \w    -69.00 -16.00   1.00    3.00    --  -42.16  57.00-180.00   53
  3  \w    -77.00  31.00   1.00    3.00    --  -42.16  19.00 120.00  108
  4  \w     63.00 129.00   1.00    3.00    --   42.16 178.00 -30.00   66
  5  \w     63.00  91.00   1.00    3.00    --   42.16 178.00  60.00   28
  6  \w     58.00 109.00   1.00   15.00    --  111.00-125.00 -30.00   51
  7  \w     52.00  90.00   1.00   15.00    --  111.00 -30.00 -90.00   38
  8  \w     43.00  98.00   1.00   15.00    --  111.00 -45.00 -30.00   55
  9  \w     63.00 121.00   1.00   15.00    --  111.00-125.00-150.00   58
 10  \w     90.00 167.00   1.00   15.00    --  111.00  45.00  90.00   77
 11  \w     39.00  93.00   1.00   15.00    --  111.00 -95.00 120.00   54
 12  \w     50.00  75.00   1.00   15.00    --  111.00 -30.00 -60.00   25
 13  \w     36.00  86.00   1.00   15.00    --  111.00 -30.00-180.00   50
 14  \w     94.00 169.00   1.00   15.00    --  111.00 125.00  90.00   75
;
_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      0.0814261000
_diffrn_orient_matrix_UB_12      0.0966165000
_diffrn_orient_matrix_UB_13      -0.0026388000
_diffrn_orient_matrix_UB_21      -0.0893349000
_diffrn_orient_matrix_UB_22      0.0705756000
_diffrn_orient_matrix_UB_23      0.0064422000
_diffrn_orient_matrix_UB_31      0.0121366000
_diffrn_orient_matrix_UB_32      0.0018586000
_diffrn_orient_matrix_UB_33      0.0775146000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0888
_diffrn_reflns_Laue_measured_fraction_full 0.857
_diffrn_reflns_Laue_measured_fraction_max 0.857
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            11700
_diffrn_reflns_point_group_measured_fraction_full 0.857
_diffrn_reflns_point_group_measured_fraction_max 0.857
_diffrn_reflns_theta_full        58.930
_diffrn_reflns_theta_max         58.930
_diffrn_reflns_theta_min         4.467
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.545
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84934
_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    1.475
_exptl_crystal_description       prism
_exptl_crystal_F_000             1472
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.38
_exptl_crystal_size_min          0.16
_refine_diff_density_max         1.992
_refine_diff_density_min         -1.406
_refine_diff_density_rms         0.176
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.139
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1029
_refine_ls_number_reflns         11700
_refine_ls_number_restraints     1171
_refine_ls_restrained_S_all      1.121
_refine_ls_R_factor_all          0.1346
_refine_ls_R_factor_gt           0.1095
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2956
_refine_ls_wR_factor_ref         0.3237
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8545
_reflns_number_total             11700
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b05577_si_002.cif
_cod_data_source_block           1-C4H8-SC-SC
_cod_database_code               4127374
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C54 H66 B1 Rh1 P2 F24'
_shelx_estimated_absorpt_t_max   0.601
_shelx_estimated_absorpt_t_min   0.317
_reflns_odcompleteness_completeness 80.13
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.561(5)
 0.439(5)
2. 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
3. Restrained distances
 F1-F2 \\sim F2-F3 \\sim F3-F1 \\sim F1-F2 \\sim F2-F3 \\sim F3-F1
 with sigma of 0.02
 C37-F1 \\sim C37-F2 \\sim C37-F3 \\sim C37-F1A \\sim C37-F3A \\sim C37-F2A
 with sigma of 0.02
 F7-F8 \\sim F7-F9 \\sim F8A-F7A \\sim F9A-F7A
 with sigma of 0.04
 C45-F7 \\sim C45-F8 \\sim C45-F9 \\sim C45-F8A \\sim C45-F9A \\sim C45-F7A
 with sigma of 0.02
 F19-F20 \\sim F19-F21 \\sim F20-F21 \\sim F21A-F20A \\sim F21A-F19A \\sim
F20A-F19A
 with sigma of 0.04
 C61-F19 \\sim C61-F20 \\sim C61-F21 \\sim C61-F21A \\sim C61-F20A \\sim
C61-F19A
 with sigma of 0.02
 F4-F5 \\sim F4-F6 \\sim F5-F6 \\sim F5A-F4A \\sim F5A-F6A \\sim F4A-F6A
 with sigma of 0.04
 C38-F4 \\sim C38-F5 \\sim C38-F6 \\sim C38-F5A \\sim C38-F4A \\sim C38-F6A
 with sigma of 0.02
 F10-F11 \\sim F10-F12 \\sim F11-F12 \\sim F11A-F12A \\sim F11A-F10A \\sim
F12A-F10A
 with sigma of 0.04
 C46-F10 \\sim C46-F11 \\sim C46-F12 \\sim C46-F11A \\sim C46-F12A \\sim
C46-F10A
 with sigma of 0.02
 F23-F22 \\sim F22-F24 \\sim F24A-F22A \\sim F24A-F23A
 with sigma of 0.04
 C62-F23 \\sim C62-F22 \\sim C62-F24 \\sim C62-F24A \\sim C62-F22A \\sim
C62-F23A
 with sigma of 0.02
 C54-F16 \\sim C54-F17 \\sim C54-F18 \\sim C54-F16A \\sim C54-F17A \\sim
C54-F18A
 with sigma of 0.02
 F13-F14 \\sim F13-F15 \\sim F14-F15 \\sim F15A-F14A \\sim F15A-F13A \\sim
F14A-F13A
 with sigma of 0.04
 C53-F13 \\sim C53-F14 \\sim C53-F15 \\sim C53-F15A \\sim C53-F14A \\sim
C53-F13A
 with sigma of 0.02
 C4A-C2A \\sim C4-C2
 with sigma of 0.02
 C3-C2 \\sim C3A-C2A
 with sigma of 0.02
 C1A-C2A \\sim C1-C2
 with sigma of 0.02
 Rh1-H3AC \\sim Rh1-H3A
 with sigma of 0.02
4. Rigid bond restraints
 C2A, C1A, C3A, C4A, C2, C1, C3, C4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C37 \\sim F1 \\sim F1A \\sim F2A \\sim F3A \\sim F2 \\sim F3: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01
C45 \\sim F7A \\sim F8A \\sim F9A \\sim F7 \\sim F8 \\sim F9: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01
C61 \\sim F19A \\sim F20A \\sim F21A \\sim F19 \\sim F20 \\sim F21: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C38 \\sim F4A \\sim F5A \\sim F6A \\sim F4 \\sim F5 \\sim F6: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01
C62 \\sim F22A \\sim F23A \\sim F24A \\sim F22 \\sim F23 \\sim F24: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C46 \\sim F10A \\sim F11A \\sim F12A \\sim F10 \\sim F11 \\sim F12: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C54 \\sim F16A \\sim F17A \\sim F18A \\sim F16 \\sim F17 \\sim F18: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C53 \\sim F13A \\sim F14A \\sim F15A \\sim F13 \\sim F14 \\sim F15: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C2A \\sim C1A \\sim C3A \\sim C4A \\sim C2 \\sim C1 \\sim C3 \\sim C4: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(F1) \\sim Ueq, Uanis(F1A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F4) \\sim Ueq, Uanis(F4A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F22) = Uanis(F22A)
Uanis(F6) = Uanis(F6A)
Uanis(F5) = Uanis(F5A)
Uanis(F18) = Uanis(F18A)
Uanis(C2) = Uanis(C2A)
Uanis(C3) = Uanis(C1A)
Uanis(C4) = Uanis(C4A)
Uanis(C1) = Uanis(C3A)
6. Rigid body (RIGU) restrains
 C37, F1, F1A, F2A, F3A, F2, F3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C45, F7A, F8A, F9A, F7, F8, F9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C61, F19A, F20A, F21A, F19, F20, F21
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C38, F4A, F5A, F6A, F4, F5, F6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C46, F10A, F11A, F12A, F10, F11, F12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C62, F22A, F23A, F24A, F22, F23, F24
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C54, F16A, F17A, F18A, F16, F17, F18
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C53, F13A, F14A, F15A, F13, F14, F15
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(2)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(2)
 Sof(F22A)=Sof(F23A)=Sof(F24A)=1-FVAR(3)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(3)
 Sof(F16A)=Sof(F17A)=Sof(F18A)=1-FVAR(4)
 Sof(F16)=Sof(F17)=Sof(F18)=FVAR(4)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=1-FVAR(5)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(5)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=1-FVAR(6)
 Sof(F19)=Sof(F20)=Sof(F21)=FVAR(6)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(7)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(7)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(8)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(8)
 Sof(C2A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=
 Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=1-FVAR(9)
 Sof(C2)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C4)=
 Sof(H4A)=Sof(H4B)=Sof(H4C)=FVAR(9)
8.a Ternary CH refined with riding coordinates:
 C25(H25), C19(H19), C13(H13), C7(H7)
8.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C30(H30A,H30B), C29(H29A,H29B), C28(H28A,H28B),
 C27(H27A,H27B), C26(H26A,H26B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B),
  C23(H23A,H23B), C24(H24A,H24B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,
 H16B), C17(H17A,H17B), C18(H18A,H18B), C12(H12A,H12B), C11(H11A,H11B),
 C10(H10A,H10B), C9(H9A,H9B), C8(H8A,H8B)
8.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)
8.d X=CH2 refined with riding coordinates:
 C1A(H1AA,H1AB), C1(H1A,H1B)
8.e Idealised Me refined as rotating group:
 C3A(H3AA,H3AB,H3AC), C4A(H4AA,H4AB,H4AC), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C)
;
_shelx_res_checksum              74678
_shelx_hkl_checksum              65996
_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 1.372
_oxdiff_exptl_absorpt_empirical_full_min 0.787