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_4127068
_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
'C54 H80 B O2 P4 Rh2, C24 H12 B Cl8, 2(C5), C Cl2'
_chemical_formula_sum            'C89 H92 B2 Cl10 O2 P4 Rh2'
_chemical_formula_weight         1899.44
_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
_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                82.527(4)
_cell_angle_beta                 85.664(3)
_cell_angle_gamma                83.694(3)
_cell_formula_units_Z            2
_cell_length_a                   14.1034(4)
_cell_length_b                   14.4749(9)
_cell_length_c                   23.9437(10)
_cell_measurement_reflns_used    10150
_cell_measurement_temperature    150.0(4)
_cell_measurement_theta_max      75.2170
_cell_measurement_theta_min      3.0450
_cell_volume                     4807.8(4)
_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      150.0(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4102
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_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    -46.00  26.00   1.00   10.00    --  -42.66  38.00  30.00   72
  2  \w    -68.00  36.00   1.00   10.00    --  -42.66  19.00 -60.00  104
  3  \w    -49.00  24.00   1.00   10.00    --  -42.66  38.00-180.00   73
  4  \w      4.00  74.00   1.00   10.00    --   42.66 -99.00 -60.00   70
  5  \w     83.00 110.00   1.00   10.00    --   42.66 178.00 -90.00   27
  6  \w     62.00 129.00   1.00   10.00    --   42.66 178.00-180.00   67
  7  \w     51.00  90.00   1.00   50.00    --  111.00 -45.00  60.00   39
  8  \w     88.00 139.00   1.00   50.00    --  111.00 -61.00  60.00   51
  9  \w     88.00 113.00   1.00   50.00    --  111.00-107.00  61.00   25
 10  \w     81.00 121.00   1.00   50.00    --  111.00-125.00  90.00   40
 11  \w     77.00 139.00   1.00   50.00    --  111.00 -77.00 150.00   62
 12  \w     66.00 109.00   1.00   50.00    --  111.00 -95.00 120.00   43
 13  \w     56.00  82.00   1.00   50.00    --  111.00 -61.00  60.00   26
 14  \w     65.00  93.00   1.00   50.00    --  111.00 -95.00   0.00   28
 15  \w     73.00 121.00   1.00   50.00    --  111.00-125.00 -30.00   48
 16  \w     72.00 111.00   1.00   50.00    --  111.00-125.00   0.00   39
 17  \w     58.00  95.00   1.00   50.00    --  111.00 -95.00-120.00   37
 18  \w     96.00 121.00   1.00   50.00    --  111.00-125.00-180.00   25
 19  \w     71.00  98.00   1.00   50.00    --  111.00 -45.00-150.00   27
 20  \w     56.00  91.00   1.00   50.00    --  111.00 -45.00-180.00   35
 21  \w     37.00  91.00   1.00   50.00    --  111.00 -30.00-150.00   54
 22  \w     87.00 165.00   1.00   50.00    --  111.00  45.00-120.00   78
 23  \w    130.00 177.00   1.00   50.00    --  111.00  45.00-150.00   47
 24  \w    142.00 169.00   1.00   50.00    --  111.00  15.00 -30.00   27
 25  \w    129.00 167.00   1.00   50.00    --  111.00 125.00-180.00   38
 26  \w     89.00 115.00   1.00   50.00    --  111.00  15.00 -30.00   26
 27  \w     88.00 177.00   1.00   50.00    --  111.00  30.00   0.00   89
 28  \w    132.00 159.00   1.00   50.00    --  111.00 125.00 120.00   27
 29  \w     96.00 124.00   1.00   50.00    --  111.00 125.00 120.00   28
 30  \w     87.00 164.00   1.00   50.00    --  111.00  30.00 120.00   77
 31  \w     39.00  90.00   1.00   50.00    --  111.00 -30.00  90.00   51
 32  \w     44.00  92.00   1.00   50.00    --  111.00 -95.00  90.00   48
 33  \w     42.00 115.00   1.00   50.00    --  111.00-125.00  60.00   73
 34  \w     42.00  82.00   1.00   50.00    --  111.00 -45.00 -90.00   40
;
_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      -0.0066546000
_diffrn_orient_matrix_UB_12      0.0959276000
_diffrn_orient_matrix_UB_13      0.0221439000
_diffrn_orient_matrix_UB_21      -0.0231868000
_diffrn_orient_matrix_UB_22      0.0490966000
_diffrn_orient_matrix_UB_23      -0.0591244000
_diffrn_orient_matrix_UB_31      -0.1074368000
_diffrn_orient_matrix_UB_32      -0.0053527000
_diffrn_orient_matrix_UB_33      0.0155342000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0913
_diffrn_reflns_av_unetI/netI     0.1029
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            46942
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.993
_diffrn_reflns_theta_min         3.095
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.293
_exptl_absorpt_correction_T_max  0.822
_exptl_absorpt_correction_T_min  0.306
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.312
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plank
_exptl_crystal_F_000             1944
_exptl_crystal_size_max          0.357
_exptl_crystal_size_mid          0.046
_exptl_crystal_size_min          0.033
_refine_diff_density_max         2.344
_refine_diff_density_min         -1.208
_refine_diff_density_rms         0.155
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1192
_refine_ls_number_reflns         18124
_refine_ls_number_restraints     575
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.1125
_refine_ls_R_factor_gt           0.0787
_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^)+(0.1285P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1904
_refine_ls_wR_factor_ref         0.2255
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12195
_reflns_number_total             18124
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b11975_si_002.cif
_cod_data_source_block           complex_14
_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_database_code               4127068
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Rh2 B2 O2 Cl10 P4 C89 H92'
_shelx_estimated_absorpt_t_max   0.819
_shelx_estimated_absorpt_t_min   0.212
_reflns_odcompleteness_completeness 98.75
_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
 Cl9-C83B = Cl10-C83B
 1.771 with sigma of 0.01
 Cl9-Cl10
 2.916 with sigma of 0.03
 Cl11-C78B = Cl12-C78B
 1.771 with sigma of 0.01
 Cl11-Cl12
 2.916 with sigma of 0.03
 C87-C86 = C86-C85 = C85-C84 = C84-C83 = C87A-C86A = C86A-C85A = C85A-C84A =
 C84A-C83A = C82-C81 = C81-C80 = C80-C79 = C79-C78 = C82A-C81A = C81A-C80A =
 C80A-C79A = C79A-C78A
 1.5 with sigma of 0.01
 C87-C85 = C85-C83 = C86-C84 = C87A-C85A = C85A-C83A = C86A-C84A = C82-C80 =
 C80-C78 = C81-C79 = C82A-C80A = C80A-C78A = C81A-C79A
 2.6 with sigma of 0.04
 C73A-C72A \\sim C73-C72 \\sim C74A-C73A \\sim C74-C73 \\sim C75A-C74A \\sim
C75-C74 \\sim C76A-C75A ~
 C76-C75 \\sim C77A-C76A \\sim C77-C76 \\sim C77-C72 \\sim C77A-C72A
 with sigma of 0.02
 Cl8A-C76A \\sim Cl8-C76 \\sim Cl7A-C74A \\sim Cl7-C74
 with sigma of 0.02
3. Restrained planarity
 C82, C81, C80, C79, C78
 with sigma of 0.1
 Cl8, C76, C77, C75, C72, C74, C73, Cl7
 with sigma of 0.1
 Cl8A, C77A, C72A, C76A, C73A, C75A, C74A, Cl7A
 with sigma of 0.1
4. Rigid bond restraints
 C78A, C79A, C80A, C81A, C82A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C82, C81, C80, C79, C78
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl11, Cl12, C78B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C83, C84, C85, C86, C87
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C87A, C86A, C85A, C84A, C83A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C82 \\sim C81 \\sim C80 \\sim C79 \\sim C78: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C77 \\sim Cl8 \\sim C76 \\sim C75 \\sim C72 \\sim C74 \\sim C73 \\sim Cl7:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C75A \\sim C77A \\sim C72A \\sim C76A \\sim C73A \\sim Cl8A \\sim C74A \\sim
Cl7A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C83B \\sim Cl9 \\sim Cl10: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Cl11 \\sim Cl12 \\sim C78B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C78A \\sim C79A \\sim C80A \\sim C81A \\sim C82A: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
C83 \\sim C84 \\sim C85 \\sim C86 \\sim C87: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C87A \\sim C86A \\sim C85A \\sim C84A \\sim C83A: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
6. Rigid body (RIGU) restrains
 C82, C81, C80, C79, C78
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C77, Cl8, C76, C75, C72, C74, C73, Cl7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C76A, C77A, C72A, C73A, C75A, Cl8A, C74A, Cl7A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C83B, Cl9, Cl10
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl11, Cl12, C78B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C78A, C79A, C80A, C81A, C82A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C83, C84, C85, C86, C87
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C87A, C86A, C85A, C84A, C83A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(C77A)=Sof(H77A)=Sof(C72A)=Sof(C73A)=Sof(H73A)=Sof(C74A)=Sof(C75A)=
 Sof(H75A)=Sof(C76A)=Sof(Cl8A)=Sof(Cl7A)=1-FVAR(1)
 Sof(Cl8)=Sof(Cl7)=Sof(C72)=Sof(C77)=Sof(H77)=Sof(C76)=Sof(C75)=Sof(H75)=
 Sof(C73)=Sof(H73)=Sof(C74)=FVAR(1)
 Fixed Sof: C87A(0.25) C86A(0.25) C85A(0.25) C84A(0.25) C83A(0.25) C82(0.75)
 C81(0.75) C80(0.75) C79(0.75) C78(0.75) Cl9(0.75) Cl10(0.75) C83B(0.75)
 Cl11(0.25) Cl12(0.25) C78B(0.25) C78A(0.25) C79A(0.25) C80A(0.25) C81A(0.25)
 C82A(0.25) C83(0.75) C84(0.75) C85(0.75) C86(0.75) C87(0.75)
8.a Ternary CH refined with riding coordinates:
 C22(H22), C1(H1), C49(H49), C25(H25), C52(H52), C31(H31), C28(H28), C4(H4)
8.b Aromatic/amide H refined with riding coordinates:
 C56(H56), C60(H60), C69(H69), C9(H9), C71(H71), C20(H20), C67(H67), C18(H18),
 C00X(H00X), C19(H19), C47(H47), C58(H58), C77(H77), C10(H10), C45(H45),
 C11(H11), C36(H36), C46(H46), C38(H38), C75(H75), C73(H73), C62(H62), C64(H64),
  C37(H37), C77A(H77A), C73A(H73A), C75A(H75A)
8.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C50(H50A,H50B,H50C), C53(H53A,H53B,H53C), C23(H23A,H23B,
 H23C), C26(H26A,H26B,H26C), C2(H2A,H2B,H2C), C54(H54A,H54B,H54C), C51(H51A,
 H51B,H51C), C27(H27A,H27B,H27C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C3(H3A,H3B,
 H3C), C29(H29A,H29B,H29C), C15(H15A,H15B,H15C), C33(H33A,H33B,H33C), C14(H14A,
 H14B,H14C), C32(H32A,H32B,H32C), C30(H30A,H30B,H30C), C41(H41A,H41B,H41C),
 C42(H42A,H42B,H42C)
;
_shelx_res_checksum              58225
_shelx_hkl_checksum              11358
_ins_header
;
TITL 157aim17 in P-1 
REM P-1 (#2 in standard setting)
CELL 1.54184  14.103391  14.474941  23.943676  82.5274  85.6645  83.6943
ZERR    2.00   0.000368   0.000862   0.001015   0.0041   0.0027   0.0032
LATT  1
SFAC C H B O P Cl Rh
UNIT 178.00 184.00 4.00 4.00 8.00 20.00 4.00
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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.053
_oxdiff_exptl_absorpt_empirical_full_min 0.600