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_4517808
_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         'C43 H35 O P2 Rh'
_chemical_formula_sum            'C43 H35 O P2 Rh'
_chemical_formula_weight         732.56
_chemical_name_systematic        Rh(DPEphos)(CH2Ph)
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-31
_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                89.848(3)
_cell_angle_beta                 77.424(3)
_cell_angle_gamma                78.168(3)
_cell_formula_units_Z            2
_cell_length_a                   11.1012(4)
_cell_length_b                   11.5775(5)
_cell_length_c                   13.3634(4)
_cell_measurement_reflns_used    6634
_cell_measurement_temperature    150.01(14)
_cell_measurement_theta_max      76.0670
_cell_measurement_theta_min      4.7460
_cell_volume                     1639.11(11)
_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      150.01(14)
_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 0.973
_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    -50.00  28.00   1.00    7.50    --  -42.53  38.00-180.00   78
  2  \w   -111.00 -22.00   1.00    7.50    --  -42.53 -57.00-120.00   89
  3  \w    -69.00  28.00   1.00    7.50    --  -42.53  57.00  30.00   97
  4  \w     57.00 129.00   1.00    7.50    --   42.53 178.00-150.00   72
  5  \w     40.00 118.00   1.00   27.50    --  111.00-125.00  60.00   78
  6  \w     64.00 136.00   1.00   27.50    --  111.00 -61.00  30.00   72
  7  \w     49.00  83.00   1.00   27.50    --  111.00 -30.00-180.00   34
  8  \w     30.00 110.00   1.00   27.50    --  111.00 -95.00-120.00   80
  9  \w     49.00 128.00   1.00   27.50    --  111.00 -61.00-120.00   79
 10  \w     43.00  91.00   1.00   27.50    --  111.00 -30.00 -90.00   48
 11  \w     30.00  98.00   1.00   27.50    --  111.00 -95.00  60.00   68
 12  \w     92.00 118.00   1.00   27.50    --  111.00-125.00-120.00   26
 13  \w     51.00 178.00   1.00   27.50    --  111.00   0.00  90.00  127
 14  \w     39.00  79.00   1.00   27.50    --  111.00-125.00-120.00   40
 15  \w     52.00  90.00   1.00   27.50    --  111.00 -30.00   0.00   38
 16  \w     40.00  68.00   1.00   27.50    --  111.00-125.00 150.00   28
 17  \w     89.00 118.00   1.00   27.50    --  111.00-125.00 150.00   29
 18  \w    116.00 174.00   1.00   27.50    --  111.00 125.00 -60.00   58
 19  \w     93.00 178.00   1.00   27.50    --  111.00  45.00 -60.00   85
;
_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      -0.0248712000
_diffrn_orient_matrix_UB_12      0.1148023000
_diffrn_orient_matrix_UB_13      0.0661169000
_diffrn_orient_matrix_UB_21      0.1428187000
_diffrn_orient_matrix_UB_22      -0.0144178000
_diffrn_orient_matrix_UB_23      -0.0077982000
_diffrn_orient_matrix_UB_31      0.0108171000
_diffrn_orient_matrix_UB_32      0.0716435000
_diffrn_orient_matrix_UB_33      -0.0977191000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0359
_diffrn_reflns_av_unetI/netI     0.0500
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            12913
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.395
_diffrn_reflns_theta_min         3.392
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.400
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84943
_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    1.484
_exptl_crystal_description       prism
_exptl_crystal_F_000             752
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.379
_refine_diff_density_min         -0.723
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.002
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     491
_refine_ls_number_reflns         6693
_refine_ls_number_restraints     414
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0420
_refine_ls_R_factor_gt           0.0358
_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^)+(0.0416P)^2^+1.1448P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0861
_refine_ls_wR_factor_ref         0.0911
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5973
_reflns_number_total             6693
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c02211_si_002.cif
_cod_data_source_block           Rh(DPEphos)(CH2Ph)
_cod_depositor_comments
'Adding full bibliography for 4517808--4517809.cif.'
_cod_database_code               4517808
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         'C54 H66 Rh1 O1 P2'
_shelx_estimated_absorpt_t_max   0.563
_shelx_estimated_absorpt_t_min   0.443
_reflns_odcompleteness_completeness 98.99
_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
2. Restrained distances
 C2A-C6A
 2.45 with sigma of 0.01
 C7A-C5A
 2.45 with sigma of 0.01
 C6A-C4A
 2.45 with sigma of 0.01
 C5A-C3A
 2.45 with sigma of 0.01
 C4A-C2A
 2.45 with sigma of 0.01
 C3A-C7A
 2.45 with sigma of 0.01
 C2A-C1A \\sim C2-C1
 with sigma of 0.02
 C4-C3 \\sim C5-C4 \\sim C6-C5 \\sim C7-C6 \\sim C7-C2 \\sim C3-C2 \\sim
C3A-C2A \\sim C3A-C4A \\sim C7A-C2A ~
 C6A-C7A \\sim C5A-C6A \\sim C4A-C5A
 with sigma of 0.02
 Rh1-C1 \\sim Rh1A-C1A
 with sigma of 0.02
 Rh1A-C2A \\sim Rh1-C2
 with sigma of 0.02
 Rh1-C3 \\sim Rh1A-C3A
 with sigma of 0.02
 Rh1A-P2 \\sim Rh1-P1
 with sigma of 0.01
 Rh1A-P1 \\sim Rh1-P2
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Rh1 \\sim Rh1A \\sim C1 \\sim C1A \\sim C2 \\sim C2A \\sim C3 \\sim C3A \\sim
C4 \\sim C4A \\sim C5 \\sim C5A \\sim C6 \\sim C6A \\sim C7 \\sim C7A: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(Rh1A) = Uanis(Rh1)
4. Rigid body (RIGU) restrains
 Rh1, Rh1A, C1, C1A, C2, C2A, C3, C3A, C4, C4A, C5, C5A, C6, C6A, C7, C7A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Rh1A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(C2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=
 Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=1-FVAR(1)
 Sof(Rh1)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=
 Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C1A(H1AA,H1AB)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C3A(H3A), C4(H4), C4A(H4A), C5(H5), C5A(H5A), C6(H6), C6A(H6A),
 C7(H7), C7A(H7A), C10(H10), C11(H11), C12(H12), C13(H13), C16(H16), C17(H17),
 C18(H18), C19(H19), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), C27(H27),
  C28(H28), C29(H29), C30(H30), C31(H31), C33(H33), C34(H34), C35(H35),
 C36(H36), C37(H37), C39(H39), C40(H40), C41(H41), C42(H42), C43(H43)
;
_shelx_res_checksum              20461
_shelx_hkl_checksum              99007
_olex2_date_sample_data_collection 2019-03-21
_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 1.244
_oxdiff_exptl_absorpt_empirical_full_min 0.785