Small bite-angle 2-phosphinophosphinine ligands enable rhodium-catalysed hydroboration of carbonyls.
Newland, Robert J.; Lynam, Jason M.; Mansell, Stephen M.; Chemical communications (Cambridge, England) 54 (2018) 5482–5485; doi:10.1039/c8cc01880d

data_7121664
_publ_section_title
;
 Small bite-angle 2-phosphinophosphinine ligands enable rhodium-catalysed
 hydroboration of carbonyls.
;
_journal_issue                   43
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              5482
_journal_page_last               5485
_journal_paper_doi               10.1039/c8cc01880d
_journal_volume                  54
_journal_year                    2018
_chemical_formula_moiety         'C29 H36 P2 Rh Si, C32 H12 B F24'
_chemical_formula_sum            'C61 H48 B F24 P2 Rh Si'
_chemical_formula_weight         1440.74
_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     direct
_audit_creation_date             2017-07-19
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2018-02-06 deposited with the CCDC.
2018-04-24 downloaded from the CCDC.
;
_cell_angle_alpha                98.298(2)
_cell_angle_beta                 102.651(2)
_cell_angle_gamma                110.657(3)
_cell_formula_units_Z            2
_cell_length_a                   13.2396(4)
_cell_length_b                   14.6179(4)
_cell_length_c                   18.0412(5)
_cell_measurement_reflns_used    21520
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      28.6590
_cell_measurement_theta_min      3.5230
_cell_volume                     3092.50(18)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.891
_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    -80.00  17.00   1.00   15.00    --   -9.43 -57.00  60.00   97
  2  \w    -88.00  27.00   1.00   15.00    --   -9.43 -19.00 150.00  115
  3  \w    -83.00  22.00   1.00   15.00    --   -9.43 -77.00-120.00  105
  4  \w    -86.00 -42.00   1.00   15.00    --   -9.43 159.00  13.00   44
  5  \w    -12.00  83.00   1.00   15.00    --   10.84  38.00  60.00   95
  6  \w    -16.00  81.00   1.00   15.00    --   10.84  57.00-180.00   97
  7  \w    -48.00  -2.00   1.00   15.00    --   10.84 -38.00-180.00   46
  8  \w      9.00  83.00   1.00   15.00    --   10.84  38.00 -90.00   74
  9  \w    -43.00  34.00   1.00   15.00    --   10.84 -57.00  90.00   77
 10  \w     -1.00  26.00   1.00   15.00    --   10.84-117.00  -9.61   27
;
_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      0.0128547000
_diffrn_orient_matrix_UB_12      -0.0182950000
_diffrn_orient_matrix_UB_13      0.0336659000
_diffrn_orient_matrix_UB_21      0.0333294000
_diffrn_orient_matrix_UB_22      -0.0206810000
_diffrn_orient_matrix_UB_23      -0.0167127000
_diffrn_orient_matrix_UB_31      0.0480260000
_diffrn_orient_matrix_UB_32      0.0457709000
_diffrn_orient_matrix_UB_33      0.0176776000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0487
_diffrn_reflns_av_unetI/netI     0.0479
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.891
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            69611
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.891
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.749
_diffrn_reflns_theta_min         2.879
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.459
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.543
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark orange'
_exptl_crystal_density_diffrn    1.547
_exptl_crystal_description       block
_exptl_crystal_F_000             1448
_exptl_crystal_size_max          0.288
_exptl_crystal_size_mid          0.223
_exptl_crystal_size_min          0.165
_refine_diff_density_max         1.463
_refine_diff_density_min         -0.960
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     896
_refine_ls_number_reflns         15721
_refine_ls_number_restraints     78
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0695
_refine_ls_R_factor_gt           0.0550
_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^)+(0.0560P)^2^+6.0540P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1258
_refine_ls_wR_factor_ref         0.1340
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13163
_reflns_number_total             15721
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc01880d2.cif
_cod_data_source_block           3
_cod_depositor_comments
'Adding full bibliography for 7121663--7121664.cif.'
_cod_original_cell_volume        3092.50(16)
_cod_database_code               7121664
_chemical_oxdiff_formula         'C61 H98 B F24 P2 Rh Si'
_chemical_oxdiff_usercomment     '@ 120 K RJN342'
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Rigid bond restraints
 C61, F22A, F22B, F23A, F23B, F24A, F24B
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(F18A) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.02
Uanis(F18B) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C61, F22A, F22B, F23A, F23B, F24A, F24B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C45, F10, F11, F12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F22B)=Sof(F23B)=Sof(F24B)=1-FVAR(1)
 Sof(F22A)=Sof(F23A)=Sof(F24A)=FVAR(1)
 Sof(F16A)=Sof(F17A)=Sof(F18A)=1-FVAR(2)
 Sof(F16B)=Sof(F17B)=Sof(F18B)=FVAR(2)
 Sof(C19B)=Sof(H19D)=Sof(H19E)=Sof(H19F)=Sof(C20B)=Sof(H20D)=Sof(H20E)=
 Sof(H20F)=Sof(C21B)=Sof(H21D)=Sof(H21E)=Sof(H21F)=1-FVAR(3)
 Sof(C19A)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C20A)=Sof(H20A)=Sof(H20B)=
 Sof(H20C)=Sof(C21A)=Sof(H21A)=Sof(H21B)=Sof(H21C)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C22(H22), C23(H23), C26(H26), C27(H27)
6.b Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C25(H25A,H25B), C28(H28A,H28B), C29(H29A,H29B)
6.c Me refined with riding coordinates:
 C19A(H19A,H19B,H19C), C19B(H19D,H19E,H19F), C20A(H20A,H20B,H20C), C20B(H20D,
 H20E,H20F), C21A(H21A,H21B,H21C), C21B(H21D,H21E,H21F)
6.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C14(H14),
 C15(H15), C16(H16), C17(H17), C18(H18), C31(H31), C33(H33), C35(H35), C39(H39),
  C41(H41), C43(H43), C47(H47), C49(H49), C51(H51), C55(H55), C57(H57), C59(H59)
6.e Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C)
;
_shelx_res_checksum              57637
_shelx_shelxl_version_number     2014/7
_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 1.279
_oxdiff_exptl_absorpt_empirical_full_min 0.727