Amine‒Borane Dehydropolymerization Using Rh-Based Precatalysts: Resting State, Chain Control, and Efficient Polymer Synthesis
Ryan, David E.; Andrea, Kori A.; Race, James J.; Boyd, Timothy M.; Lloyd-Jones, Guy C.; Weller, Andrew S.; ACS Catalysis  (2020) 7443–7448; doi:10.1021/acscatal.0c02211

data_4517809
_publ_section_title
;
 Amine--Borane Dehydropolymerization Using Rh-Based Precatalysts: Resting
 State, Chain Control, and Efficient Polymer Synthesis
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              7443
_journal_page_last               7448
_journal_paper_doi               10.1021/acscatal.0c02211
_journal_year                    2020
_chemical_formula_moiety         'C46 H39 O P2 Rh, 0.85(C6 H6)'
_chemical_formula_sum            'C51.1 H44.1 O P2 Rh'
_chemical_formula_weight         838.95
_chemical_name_systematic        Rh(Xantphos)(CH2Ph)
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-08-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-05-14 deposited with the CCDC.	2020-05-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.216(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.1346(11)
_cell_length_b                   10.4118(3)
_cell_length_c                   24.8442(14)
_cell_measurement_reflns_used    3555
_cell_measurement_temperature    149.99(16)
_cell_measurement_theta_max      74.2330
_cell_measurement_theta_min      4.5950
_cell_volume                     4130.7(4)
_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      149.99(16)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4102
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.978
_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    -73.00  31.00   1.00    5.00    --  -42.16  77.00 -30.00  104
  2  \w     -9.00  19.00   1.00    5.00    --  -42.16  38.00-180.00   28
  3  \w    -48.00  30.00   1.00    5.00    --  -42.16  38.00-120.00   78
  4  \w     89.00 124.00   1.00    5.00    --   42.16 178.00-180.00   35
  5  \w     89.00 124.00   1.00   32.50    --  111.00  45.00  90.00   35
  6  \w    126.00 173.00   1.00   32.50    --  111.00  45.00  90.00   47
  7  \w     46.00  97.00   1.00   32.50    --  111.00 -45.00 -30.00   51
  8  \w     48.00  91.00   1.00   32.50    --  111.00 -30.00 150.00   43
  9  \w     41.00 105.00   1.00   32.50    --  111.00 -95.00   0.00   64
 10  \w     97.00 171.00   1.00   32.50    --  111.00  45.00  60.00   74
 11  \w     51.00  92.00   1.00   32.50    --  111.00 -45.00-180.00   41
 12  \w     89.00 140.00   1.00   32.50    --  111.00  30.00   0.00   51
 13  \w    144.00 178.00   1.00   32.50    --  111.00  30.00   0.00   34
 14  \w     49.00  96.00   1.00   32.50    --  111.00 -45.00 120.00   47
 15  \w     44.00  85.00   1.00   32.50    --  111.00 -61.00 -30.00   41
 16  \w     36.00  78.00   1.00   32.50    --  111.00 -30.00-150.00   42
 17  \w     34.00  69.00   1.00   32.50    --  111.00 -15.00  90.00   35
 18  \w    122.00 147.00   1.00   32.50    --  111.00 -15.00  90.00   25
 19  \w     45.00  89.00   1.00   32.50    --  111.00 -30.00  30.00   44
 20  \w     96.00 157.00   1.00   32.50    --  111.00  30.00  30.00   61
;
_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      0.0653646000
_diffrn_orient_matrix_UB_12      0.0569677000
_diffrn_orient_matrix_UB_13      -0.0329117000
_diffrn_orient_matrix_UB_21      -0.0707615000
_diffrn_orient_matrix_UB_22      0.0619025000
_diffrn_orient_matrix_UB_23      -0.0396857000
_diffrn_orient_matrix_UB_31      0.0055598000
_diffrn_orient_matrix_UB_32      0.1218267000
_diffrn_orient_matrix_UB_33      0.0354869000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0815
_diffrn_reflns_av_unetI/netI     0.0929
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            22824
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.594
_diffrn_reflns_theta_min         3.595
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.356
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73093
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.349
_exptl_crystal_description       block
_exptl_crystal_F_000             1735
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.196
_refine_diff_density_min         -2.220
_refine_diff_density_rms         0.134
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     572
_refine_ls_number_reflns         8496
_refine_ls_number_restraints     274
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.1372
_refine_ls_R_factor_gt           0.0994
_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^)+(0.1760P)^2^+5.4906P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2612
_refine_ls_wR_factor_ref         0.3060
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5457
_reflns_number_total             8496
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c02211_si_002.cif
_cod_data_source_block           Rh(Xantphos)(CH2Ph)
_cod_depositor_comments
'Adding full bibliography for 4517808--4517809.cif.'
_cod_original_formula_sum        'C51.10 H44.10 O P2 Rh'
_cod_database_code               4517809
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H50 Rh1 P2 O1'
_reflns_odcompleteness_completeness 99.31
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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
 C51-C50 \\sim C50-C49 \\sim C49-C48 \\sim C48-C47 \\sim C47-C52 \\sim C52-C51
 with sigma of 0.02
 C51-C47 \\sim C51-C47 \\sim C48-C50 \\sim C48-C52 \\sim C52-C50 \\sim C47-C49
 with sigma of 0.04
3. Restrained planarity
 C51, C50, C49, C48, C47, C52
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C2 \\sim C7 \\sim C3 \\sim C1 \\sim C6 \\sim C5 \\sim C4: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C7A \\sim C6A \\sim C5A \\sim C4A \\sim C3A \\sim C2A \\sim C1A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C51 \\sim C50 \\sim C49 \\sim C48 \\sim C47 \\sim C52: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
5. Rigid body (RIGU) restrains
 C2, C7, C3, C1, C6, C5, C4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7A, C6A, C5A, C4A, C3A, C2A, C1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C51, C50, C49, C48, C47, C52
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C7A)=Sof(H7A)=Sof(C6A)=Sof(H6A)=Sof(C5A)=Sof(H5A)=Sof(C4A)=Sof(H4A)=
 Sof(C3A)=Sof(H3A)=Sof(C2A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=1-FVAR(1)
 Sof(C2)=Sof(C7)=Sof(H7)=Sof(C3)=Sof(H3)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C6)=
 Sof(H6)=Sof(C5)=Sof(H5)=Sof(C4)=Sof(H4)=FVAR(1)
 Sof(C51)=Sof(H51)=Sof(C50)=Sof(H50)=Sof(C49)=Sof(H49)=Sof(C48)=Sof(H48)=
 Sof(C47)=Sof(H47)=Sof(C52)=Sof(H52)=FVAR(2)
7.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B)
7.b Aromatic/amide H refined with riding coordinates:
 C35(H35), C33(H33), C34(H34), C9(H9), C31(H31), C45(H45), C27(H27), C30(H30),
 C10(H10), C44(H44), C13(H13), C43(H43), C25(H25), C28(H28), C29(H29), C23(H23),
  C19(H19), C7(H7), C24(H24), C11(H11), C12(H12), C3(H3), C22(H22), C21(H21),
 C17(H17), C18(H18), C15(H15), C6(H6), C16(H16), C5(H5), C4(H4), C7A(H7A),
 C6A(H6A), C5A(H5A), C4A(H4A), C3A(H3A), C51(H51), C50(H50), C49(H49), C48(H48),
  C47(H47), C52(H52)
7.c X=CH2 refined with riding coordinates:
 C1A(H1AA,H1AB)
7.d Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C39(H39A,H39B,H39C)
;
_shelx_res_checksum              55400
_shelx_hkl_checksum              14633
_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 1.566
_oxdiff_exptl_absorpt_empirical_full_min 0.723