Ortho-aryl substituted DPEphos ligands: Rhodium Complexes Featuring C‒H Anagostic Interactions and B‒H Agostic Bonds.
Race, James; Burnage, Arron; Boyd, Timothy M.; Heyam, Alex; Martinez-Martinez, Antonio J.; Macgregor, Stuart Alan; Weller, Andrew S.; Chemical Science  (2021) –; doi:10.1039/D1SC01430G

data_1562852
_publ_section_title
;
 Ortho-aryl substituted DPEphos ligands: Rhodium Complexes Featuring C--H
 Anagostic Interactions and B--H Agostic Bonds.
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC01430G
_journal_year                    2021
_chemical_formula_moiety         'C47 H44 O5 P2 Rh, C32 H12 B F24'
_chemical_formula_sum            'C79 H56 B F24 O5 P2 Rh'
_chemical_formula_weight         1716.89
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-09-18
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2021-02-21 deposited with the CCDC.	2021-05-25 downloaded from the CCDC.
;
_cell_angle_alpha                82.461(3)
_cell_angle_beta                 84.317(3)
_cell_angle_gamma                84.684(3)
_cell_formula_units_Z            2
_cell_length_a                   12.9929(4)
_cell_length_b                   16.2926(6)
_cell_length_c                   17.9735(6)
_cell_measurement_reflns_used    18461
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      76.5410
_cell_measurement_theta_min      2.4820
_cell_volume                     3741.1(2)
_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 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.15
_diffrn_detector_area_resol_mean 10.5035
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.985
_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  41.00   1.00    1.00    --    0.00 -99.00 -30.00   39
  2  \w     39.00  91.00   1.00    1.00    --    0.00  57.00 120.00   52
  3  \w    -42.00  29.00   1.00    1.00    --    0.00  57.00 120.00   71
  4  \w     10.00  38.00   1.00    1.00    --    0.00 -99.00 -90.00   28
  5  \w    -83.00 -26.00   1.00    4.00    --  -60.50 125.00 150.00   57
  6  \w    107.00 142.00   1.00    4.00    --   60.50 125.00-180.00   35
  7  \w    116.00 151.00   1.00    4.00    --   60.50 125.00-150.00   35
  8  \w    113.00 150.00   1.00    4.00    --   60.50 125.00 -90.00   37
  9  \w     58.00 117.00   1.00    4.00    --   60.50-125.00  30.00   59
 10  \w    -20.00  96.00   1.00    4.00    --   60.50 -45.00 -90.00  116
 11  \w    115.00 152.00   1.00    4.00    --   60.50 125.00  30.00   37
 12  \w    -28.00 156.00   1.00    4.00    --   60.50 -15.00  30.00  184
 13  \w     95.00 129.00   1.00    4.00    --   60.50 125.00   0.00   34
 14  \w     30.00 112.00   1.00   12.00    --  121.00-111.00  90.00   82
 15  \w     33.00  85.00   1.00   12.00    --  121.00-111.00 120.00   52
 16  \w    134.00 176.00   1.00   12.00    --  121.00  37.00   0.00   42
 17  \w     25.00 137.00   1.00   12.00    --  121.00 -91.00-120.00  112
 18  \w     74.00 110.00   1.00   12.00    --  121.00  37.00   0.00   36
 19  \w     35.00 105.00   1.00   12.00    --  121.00 -50.00-150.00   70
 20  \w    110.00 177.00   1.00   12.00    --  121.00  37.00 -60.00   67
 21  \w     35.00 111.00   1.00   12.00    --  121.00-111.00   0.00   76
 22  \w    146.00 172.00   1.00   12.00    --  121.00  63.00-150.00   26
 23  \w     57.00  88.00   1.00   12.00    --  121.00-111.00-180.00   31
 24  \w     70.00 111.00   1.00   12.00    --  121.00-111.00-120.00   41
 25  \w    120.00 150.00   1.00   12.00    --  121.00 178.00 150.00   30
 26  \w     52.00  80.00   1.00   12.00    --  121.00 -25.00 -30.00   28
 27  \w    108.00 164.00   1.00   12.00    --  121.00  37.00-120.00   56
 28  \w    109.00 171.00   1.00   12.00    --  121.00  63.00 -30.00   62
 29  \w     62.00  87.00   1.00   12.00    --  121.00 178.00 150.00   25
 30  \w     74.00 101.00   1.00   12.00    --  121.00 178.00 120.00   27
 31  \w     68.00  99.00   1.00   12.00    --  121.00 -63.00-120.00   31
 32  \w     45.00  76.00   1.00   12.00    --  121.00 -37.00  90.00   31
 33  \w    100.00 153.00   1.00   12.00    --  121.00 111.00  60.00   53
 34  \w    116.00 142.00   1.00   12.00    --  121.00 178.00 120.00   26
 35  \w    120.00 164.00   1.00   12.00    --  121.00 -63.00-120.00   44
 36  \w     29.00 112.00   1.00   12.00    --  121.00-111.00 150.00   83
 37  \w    104.00 175.00   1.00   12.00    --  121.00  50.00 -90.00   71
 38  \w     80.00 111.00   1.00   12.00    --  121.00  63.00-150.00   31
 39  \w     30.00  88.00   1.00   12.00    --  121.00 -50.00 -30.00   58
 40  \w     29.00 112.00   1.00   12.00    --  121.00-106.00-160.05   83
 41  \w    -87.00 -70.00   1.00    4.00    --  -60.50  15.00 -13.00   17
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0252
_diffrn_reflns_av_unetI/netI     0.0325
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            34319
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.600
_diffrn_reflns_theta_min         2.489
_exptl_absorpt_coefficient_mu    3.246
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87845
_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    1.524
_exptl_crystal_description       prism
_exptl_crystal_F_000             1732
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.721
_refine_diff_density_min         -0.486
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1304
_refine_ls_number_reflns         15530
_refine_ls_number_restraints     1441
_refine_ls_restrained_S_all      1.105
_refine_ls_R_factor_all          0.0435
_refine_ls_R_factor_gt           0.0409
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0634P)^2^+2.3767P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1092
_refine_ls_wR_factor_ref         0.1115
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14494
_reflns_number_total             15530
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01430g3.cif
_cod_data_source_block           2-OMe
_cod_database_code               1562852
_publcif_datablock.id            {cf3239ef-8c7f-4f04-af36-c589c47da90e}
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.625
_shelx_estimated_absorpt_t_min   0.535
_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
 F13-F14 \\sim F13-F15 \\sim F14-F15 \\sim F13A-F14A \\sim F13A-F15A \\sim
F14A-F15A
 with sigma of 0.04
 C54-F13 \\sim C54-F14 \\sim C54-F15 \\sim C54-F13A \\sim C54-F14A \\sim
C54-F15A
 with sigma of 0.02
 F2-F3 \\sim F2-F1 \\sim F3A-F2A \\sim F3A-F1A \\sim F2A-F1A \\sim F3-F1
 with sigma of 0.04
 C78-F2 \\sim C78-F3A \\sim C78-F2A \\sim C78-F3 \\sim C78-F1A \\sim C78-F1
 with sigma of 0.02
 F4-F5 \\sim F4-F6 \\sim F4A-F5A \\sim F4A-F6A \\sim F5-F6 \\sim F5A-F6A
 with sigma of 0.04
 C75-F4 \\sim C75-F4A \\sim C75-F5 \\sim C75-F5A \\sim C75-F6A \\sim C75-F6
 with sigma of 0.02
 F12-F10 \\sim F12-F11 \\sim F12A-F10A \\sim F12A-F11A \\sim F10-F11 \\sim
F10A-F11A
 with sigma of 0.04
 C59-F12 \\sim C59-F12A \\sim C59-F10 \\sim C59-F10A \\sim C59-F11 \\sim
C59-F11A
 with sigma of 0.02
 F8A-F7A \\sim F8A-F9A \\sim F8-F7 \\sim F8-F9 \\sim F7-F9 \\sim F7A-F9A
 with sigma of 0.04
 C62-F8A \\sim C62-F8 \\sim C62-F7 \\sim C62-F7A \\sim C62-F9 \\sim C62-F9A
 with sigma of 0.02
 O2A-C5A \\sim O2-C5
 with sigma of 0.02
 O2A-C44A \\sim O2-C44
 with sigma of 0.02
 O1-C18 \\sim O1-C18A
 with sigma of 0.02
 C17-C18 \\sim C17A-C18A \\sim C17-C16 \\sim C17A-C16A \\sim C16-C15 \\sim
C16A-C15A \\sim C15-C14 ~
 C15A-C14A \\sim C14-C13 \\sim C13-C18
 with sigma of 0.02
 O5A-C46A \\sim O5-C46
 with sigma of 0.02
 O5-C30 \\sim O5A-C30
 with sigma of 0.02
 O3A-C12 \\sim O3-C12
 with sigma of 0.02
 O3A-C45A \\sim O3-C45
 with sigma of 0.02
 C1A-C2A \\sim C2A-C3A \\sim C2-C3 \\sim C1-C2 \\sim C1-C6 \\sim C5-C6 \\sim
C4A-C5A \\sim C4-C5 \\sim C3A-C4A
 \\sim C3-C4
 with sigma of 0.02
 C5-C6 \\sim C5A-C6 \\sim C1-C6 \\sim C1A-C6
 with sigma of 0.02
 C14-C13 \\sim C14A-C13 \\sim C13-C18 \\sim C13-C18A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F13 \\sim F13A \\sim F14 \\sim F14A \\sim F15 \\sim F15A \\sim C54: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01 within 2A
F1 \\sim F1A \\sim F2 \\sim F2A \\sim F3 \\sim F3A \\sim C78: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01 within 2A
F4 \\sim F4A \\sim F5 \\sim F5A \\sim F6 \\sim F6A \\sim C75: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01 within 2A
F10 \\sim F10A \\sim F11 \\sim F11A \\sim F12 \\sim F12A \\sim C59: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01 within 2A
F7 \\sim F7A \\sim F8 \\sim F8A \\sim F9 \\sim F9A \\sim C62: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01 within 2A
C18 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18A \\sim C14A
\\sim C15A \\sim C16A \\sim C17A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.01 within 2A
O5 \\sim C46 \\sim O5A \\sim C46A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.01 within 2A
O3A \\sim C45A \\sim O3 \\sim C45: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.01 within 2A
O2 \\sim C6 \\sim C5 \\sim C4 \\sim C3 \\sim C2 \\sim C1 \\sim C44 \\sim O2A
\\sim C5A \\sim C4A \\sim C3A \\sim C2A \\sim C1A \\sim C44A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01 within 2A
4. Rigid body (RIGU) restrains
 F13, F13A, F14, F14A, F15, F15A, C54
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1, F1A, F2, F2A, F3, F3A, C78
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F4, F4A, F5, F5A, F6, F6A, C75
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F10, F10A, F11, F11A, F12, F12A, C59
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F7, F7A, F8, F8A, F9, F9A, C62
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C18, C13, C14, C15, C16, C17, C18A, C14A, C15A, C16A, C17A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O5, C46, O5A, C46A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O3A, C45A, O3, C45
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O2, C6, C5, C4, C3, C2, C1, C44, O2A, C5A, C4A, C3A, C2A, C1A, C44A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F13A)=Sof(F14A)=Sof(F15A)=1-FVAR(1)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(1)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(2)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(2)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(3)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(3)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(4)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(4)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(5)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(5)
 Sof(O2A)=Sof(C5A)=Sof(C4A)=Sof(H4A)=Sof(C3A)=Sof(H3A)=Sof(C2A)=Sof(H2A)=
 Sof(C1A)=Sof(H1A)=Sof(C44A)=Sof(H44D)=Sof(H44E)=Sof(H44F)=1-FVAR(6)
 Sof(O2)=Sof(C5)=Sof(C4)=Sof(H4)=Sof(C3)=Sof(H3)=Sof(C2)=Sof(H2)=Sof(C1)=
 Sof(H1)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=FVAR(6)
 Sof(C18A)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(H16A)=
 Sof(C17A)=Sof(H17A)=1-FVAR(7)
 Sof(C18)=Sof(C14)=Sof(H14)=Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16)=Sof(C17)=
 Sof(H17)=FVAR(7)
 Sof(O5A)=Sof(C46A)=Sof(H46D)=Sof(H46E)=Sof(H46F)=1-FVAR(8)
 Sof(O5)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=FVAR(8)
 Sof(O3A)=Sof(C45A)=Sof(H45A)=Sof(H45B)=Sof(H45C)=1-FVAR(9)
 Sof(O3)=Sof(C45)=Sof(H45D)=Sof(H45E)=Sof(H45F)=FVAR(9)
6.a Ternary CH refined with riding coordinates:
 C37(H37), C38(H38), C39(H39), C40(H40), C41(H41), C42(H42)
6.b Secondary CH2 refined with riding coordinates:
 C43(H43A,H43B)
6.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C21(H21), C22(H22), C23(H23), C14(H14), C15(H15), C16(H16),
 C17(H17), C4(H4), C3(H3), C2(H2), C1(H1), C11(H11), C10(H10), C9(H9), C8(H8),
 C35(H35), C34(H34), C33(H33), C32(H32), C29(H29), C28(H28), C27(H27), C26(H26),
  C57(H57), C79(H79), C76(H76), C73(H73), C63(H63), C60(H60), C55(H55),
 C52(H52), C49(H49), C71(H71), C68(H68), C65(H65), C4A(H4A), C3A(H3A), C2A(H2A),
  C1A(H1A), C14A(H14A), C15A(H15A), C16A(H16A), C17A(H17A)
6.d Idealised Me refined as rotating group:
 C44(H44A,H44B,H44C), C45A(H45A,H45B,H45C), C47(H47A,H47B,H47C), C46(H46A,H46B,
 H46C), C44A(H44D,H44E,H44F), C46A(H46D,H46E,H46F), C45(H45D,H45E,H45F)
;
_shelx_res_checksum              22424
_shelx_hkl_checksum              58531
_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
;
_publcif_funding_html
;
;