Dehydropolymerization of H3B·NMeH2 To Form Polyaminoboranes Using [Rh(Xantphos-alkyl)] Catalysts.
Adams, Gemma M.; Colebatch, Annie L.; Skornia, Joseph T.; McKay, Alasdair I.; Johnson, Heather C.; Lloyd Jones, Guy C.; Macgregor, Stuart A.; Beattie, Nicholas A.; Weller, Andrew S.; Journal of the American Chemical Society  (2018) –; doi:10.1021/jacs.7b11975

data_4127067
_publ_section_title
;
 Dehydropolymerization of H3B&#x00B7;NMeH2 To Form Polyaminoboranes Using
 [Rh(Xantphos-alkyl)] Catalysts.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b11975
_journal_year                    2018
_chemical_formula_moiety         'C33 H43 F2 O P2 Rh, 2(C6 H6)'
_chemical_formula_sum            'C45 H55 F2 O P2 Rh'
_chemical_formula_weight         814.74
_space_group_crystal_system      monoclinic
_space_group_IT_number           11
_space_group_name_Hall           '-P 2yb'
_space_group_name_H-M_alt        'P 1 21/m 1'
_symmetry_space_group_name_Hall  '-P 2yb'
_symmetry_space_group_name_H-M   'P 1 21/m 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-10-13
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 113.521(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.9582(5)
_cell_length_b                   14.5158(4)
_cell_length_c                   13.0659(5)
_cell_measurement_reflns_used    5836
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      76.2140
_cell_measurement_theta_min      4.1880
_cell_volume                     2079.58(15)
_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      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 0.988
_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    -38.00  27.00   1.00    1.00    --  -41.65  37.00  30.00   65
  2  \w    -46.00  20.00   1.00    1.00    --  -41.65  37.00 -30.00   66
  3  \w    -27.00  31.00   1.00    1.00    --  -41.65  37.00-120.00   58
  4  \w    -16.00  19.00   1.00    1.00    --  -41.65  37.00-180.00   35
  5  \w     63.00  88.00   1.00    1.00    --   41.65-125.00 -90.00   25
  6  \w     49.00  75.00   1.00    2.00    --  111.00 -30.00 -30.00   26
  7  \w     48.00  90.00   1.00    2.00    --  111.00 -45.00 -30.00   42
  8  \w     48.00  84.00   1.00    2.00    --  111.00 -30.00  60.00   36
  9  \w     64.00  96.00   1.00    2.00    --  111.00 -45.00  90.00   32
 10  \w     64.00 108.00   1.00    2.00    --  111.00 -94.00 150.00   44
 11  \w     52.00  78.00   1.00    2.00    --  111.00 -45.00 150.00   26
 12  \w     36.00  86.00   1.00    2.00    --  111.00 -30.00 150.00   50
 13  \w     46.00  97.00   1.00    2.00    --  111.00 -45.00  30.00   51
 14  \w     44.00  72.00   1.00    2.00    --  111.00 -45.00 -60.00   28
 15  \w     41.00  84.00   1.00    2.00    --  111.00 -45.00-150.00   43
 16  \w    103.00 153.00   1.00    2.00    --  111.00  30.00  30.00   50
 17  \w    115.00 141.00   1.00    2.00    --  111.00  77.00  60.00   26
 18  \w    152.00 177.00   1.00    2.00    --  111.00 125.00 150.00   25
 19  \w     94.00 120.00   1.00    2.00    --  111.00 125.00-120.00   26
 20  \w    147.00 175.00   1.00    2.00    --  111.00 125.00-120.00   28
 21  \w    149.00 176.00   1.00    2.00    --  111.00 125.00-180.00   27
 22  \w     97.00 144.00   1.00    2.00    --  111.00 125.00-180.00   47
;
_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      -0.0467597000
_diffrn_orient_matrix_UB_12      -0.0578702000
_diffrn_orient_matrix_UB_13      -0.1078839000
_diffrn_orient_matrix_UB_21      0.1325184000
_diffrn_orient_matrix_UB_22      -0.0174409000
_diffrn_orient_matrix_UB_23      0.0140673000
_diffrn_orient_matrix_UB_31      0.0045501000
_diffrn_orient_matrix_UB_32      -0.0871772000
_diffrn_orient_matrix_UB_33      0.0685326000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0245
_diffrn_reflns_av_unetI/netI     0.0276
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            11018
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.181
_diffrn_reflns_theta_min         3.689
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.370
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84590
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.301
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             852
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.13
_refine_diff_density_max         1.030
_refine_diff_density_min         -0.835
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     340
_refine_ls_number_reflns         4481
_refine_ls_number_restraints     443
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0302
_refine_ls_R_factor_gt           0.0280
_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^)+(0.0391P)^2^+0.9144P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0716
_refine_ls_wR_factor_ref         0.0730
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4220
_reflns_number_total             4481
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b11975_si_002.cif
_cod_data_source_block           complex_12
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_crystal_density_meas' value 'not measured' was changed to '?'
- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 
;
_cod_original_cell_volume        2079.57(14)
_cod_database_code               4127067
_shelx_shelxl_version_number     2014/7
_publ_section_exptl
;
Any special experimental details
;
_chemical_oxdiff_formula         'Rh1 P2 O1 F2 C33 H43'
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C18-F2 \\sim C17-F1
 with sigma of 0.02
 C18-C19 \\sim C20-C19 \\sim C18-C17 \\sim C21-C20 \\sim C16-C21 \\sim C17-C16
 with sigma of 0.02
 C18-F1 \\sim C16-F1 \\sim C17-F2 \\sim C19-F2
 with sigma of 0.04
 C21-C19 \\sim C16-C20 \\sim C17-C21 \\sim C18-C16 \\sim C17-C19 \\sim C18-C20
 with sigma of 0.04
 C18A-F2A \\sim C17A-F1A
 with sigma of 0.02
 C18A-C19A \\sim C20A-C19A \\sim C18A-C17A \\sim C21A-C20A \\sim C16A-C21A
\\sim C17A-C16A
 with sigma of 0.02
 C18A-F1A \\sim C16A-F1A \\sim C17A-F2A \\sim C19A-F2A
 with sigma of 0.04
 C21A-C19A \\sim C16A-C20A \\sim C17A-C21A \\sim C18A-C16A \\sim C17A-C19A
\\sim C18A-C20A
 with sigma of 0.04
 Rh1-C16A \\sim Rh1-C16
 with sigma of 0.02
 C26-C25 \\sim C25-C24 \\sim C24-C23 \\sim C27-C26 \\sim C22-C27 \\sim C22-C23
 with sigma of 0.02
 C23-C25 \\sim C23-C27 \\sim C27-C25 \\sim C22-C26 \\sim C22-C24 \\sim C24-C26
 with sigma of 0.04
 C29-C28 \\sim C30-C29 \\sim C30A_$1-C29A_$1 \\sim C29A_$1-C28A_$1
 with sigma of 0.02
 C28-C30 \\sim C28A_$1-C30A_$1
 with sigma of 0.04
3. Restrained planarity
 C18, C17, C16, C21, C20, C19, F2, F1
 with sigma of 0.1
 C18A, C17A, C16A, C21A, C20A, C19A, F2A, F1A
 with sigma of 0.1
 C26, C25, C24, C23, C27, C22
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C18 \\sim C17 \\sim C16 \\sim C21 \\sim C20 \\sim C19 \\sim F2 \\sim F1: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C18A \\sim C17A \\sim C16A \\sim C21A \\sim C20A \\sim C19A \\sim F2A \\sim
F1A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C26 \\sim C25 \\sim C24 \\sim C23 \\sim C27 \\sim C22: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
C28 \\sim C29 \\sim C30: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C28A \\sim C29A \\sim C30A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
5. Rigid body (RIGU) restrains
 C18, C17, C16, C21, C20, C19, F2, F1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C18A, C17A, C16A, C21A, C20A, C19A, F2A, F1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26, C25, C24, C23, C27, C22
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C28, C29, C30
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C28A, C29A, C30A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C18A)=Sof(C17A)=Sof(C16A)=Sof(C21A)=Sof(H21A)=Sof(C20A)=Sof(H20A)=
 Sof(C19A)=Sof(H19A)=Sof(F2A)=Sof(F1A)=0.5*(1-FVAR(2))
 Sof(C18)=Sof(C17)=Sof(C16)=Sof(C21)=Sof(H21)=Sof(C20)=Sof(H20)=Sof(C19)=
 Sof(H19)=Sof(F2)=Sof(F1)=0.5*FVAR(2)
 Sof(C29A)=Sof(H29A)=Sof(C28A)=Sof(H28A)=Sof(C30A)=Sof(H30A)=1-FVAR(2)
 Sof(C29)=Sof(H29)=Sof(C30)=Sof(H30)=Sof(C28)=Sof(H28)=FVAR(2)
 Fixed Sof: H15A(0.5) H15B(0.5) H15C(0.5) H14A(0.5) H14B(0.5) H14C(0.5)
7.a Ternary CH refined with riding coordinates:
 C2(H2), C4(H4)
7.b Me refined with riding coordinates:
 C15(H15A,H15B,H15C), C14(H14A,H14B,H14C)
7.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C22(H22), C21(H21), C20(H20), C19(H19),
 C21A(H21A), C20A(H20A), C19A(H19A), C26(H26), C25(H25), C24(H24), C23(H23),
 C27(H27), C29(H29), C30(H30), C28(H28), C29A(H29A), C28A(H28A), C30A(H30A)
7.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C)
;
_shelx_res_checksum              37373
_shelx_hkl_checksum              43887
_ins_header
;
TITL 070aim16 in P2(1)/m 
REM P2(1)/m (#11 in standard setting)
CELL 1.54184  11.958174  14.515785  13.065858  90.0000 113.5207  90.0000
ZERR    3.00   0.000467   0.000389   0.000472   0.0000   0.0045   0.0000
LATT  1
SYMM -x, y+1/2,-z 
SFAC C H O F P Rh
UNIT 99.00 129.00 3.00 6.00 6.00 3.00
TREF
HKLF 4
END
;
_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 1.198
_oxdiff_exptl_absorpt_empirical_full_min 0.891