The role of neutral Rh(PONOP)H, free NMe<sub>2</sub>H, boronium and ammonium salts in the dehydrocoupling of dimethylamine-borane using the cationic pincer [Rh(PONOP)(η<sup>2</sup>-H<sub>2</sub>)]<sup>+</sup> catalyst.
Spearing-Ewyn, E Anastasia K; Beattie, Nicholas A.; Colebatch, Annie L.; Martinez-Martinez, Antonio J; Docker, Andrew; Boyd, Timothy M.; Baillie, Gregg; Reed, Rachel; Macgregor, Stuart A.; Weller, Andrew S.; Dalton transactions (Cambridge, England : 2003) 48 (2019) 14724–14736; doi:10.1039/c9dt03358k

data_7701212
_publ_section_title
;
 The role of neutral Rh(PONOP)H, free NMe<sub>2</sub>H, boronium and
 ammonium salts in the dehydrocoupling of dimethylamine-borane using the
 cationic pincer [Rh(PONOP)(\h<sup>2</sup>-H<sub>2</sub>)]<sup>+</sup>
 catalyst.
;
_journal_issue                   39
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              14724
_journal_page_last               14736
_journal_paper_doi               10.1039/c9dt03358k
_journal_volume                  48
_journal_year                    2019
_chemical_formula_moiety         'C21 H40 N O2 P2 Rh'
_chemical_formula_sum            'C21 H40 N O2 P2 Rh'
_chemical_formula_weight         503.39
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-06-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-05-20 deposited with the CCDC.    2019-09-03 downloaded from the CCDC.
;
_cell_angle_alpha                68.569(2)
_cell_angle_beta                 89.805(2)
_cell_angle_gamma                88.2210(10)
_cell_formula_units_Z            12
_cell_length_a                   9.2325(2)
_cell_length_b                   26.6707(4)
_cell_length_c                   33.1426(6)
_cell_measurement_reflns_used    23609
_cell_measurement_temperature    150.01(15)
_cell_measurement_theta_max      76.1050
_cell_measurement_theta_min      3.9710
_cell_volume                     7592.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_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(15)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4102
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_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  30.00   1.00    3.75    --  -42.66  38.00 150.00   80
  2  \w    -88.00 -40.00   1.00    3.75    --  -42.66 178.00-180.00   48
  3  \w   -120.00  -7.00   1.00    3.75    --  -42.66 -19.00 -30.00  113
  4  \w     58.00 129.00   1.00    3.75    --   42.66 178.00 -60.00   71
  5  \w     85.00 129.00   1.00    3.75    --   42.66 178.00 120.00   44
  6  \w     57.00  98.00   1.00    3.75    --   42.66 178.00  30.00   41
  7  \w     44.00  91.00   1.00   15.00    --  111.00 -30.00 -90.00   47
  8  \w     77.00 121.00   1.00   15.00    --  111.00-125.00-180.00   44
  9  \w     78.00 107.00   1.00   15.00    --  111.00 -61.00-180.00   29
 10  \w     52.00  78.00   1.00   15.00    --  111.00 -30.00 -30.00   26
 11  \w    112.00 157.00   1.00   15.00    --  111.00  30.00 150.00   45
 12  \w    113.00 166.00   1.00   15.00    --  111.00 125.00-180.00   53
 13  \w     40.00  66.00   1.00   15.00    --  111.00 -95.00-150.00   26
 14  \w     39.00  71.00   1.00   15.00    --  111.00-125.00 120.00   32
 15  \w     87.00 121.00   1.00   15.00    --  111.00-125.00   0.00   34
 16  \w     48.00  73.00   1.00   15.00    --  111.00-125.00-180.00   25
 17  \w    107.00 155.00   1.00   15.00    --  111.00 125.00 -60.00   48
 18  \w     90.00 121.00   1.00   15.00    --  111.00-125.00  90.00   31
 19  \w     50.00 100.00   1.00   15.00    --  111.00 -95.00   0.00   50
 20  \w     31.00 108.00   1.00   15.00    --  111.00 -95.00 120.00   77
 21  \w     95.00 153.00   1.00   15.00    --  111.00 -15.00-120.00   58
 22  \w     39.00 109.00   1.00   15.00    --  111.00 -95.00-120.00   70
 23  \w     36.00  91.00   1.00   15.00    --  111.00 -30.00-150.00   55
 24  \w     41.00  78.00   1.00   15.00    --  111.00 -45.00  90.00   37
 25  \w    101.00 140.00   1.00   15.00    --  111.00  77.00   0.00   39
 26  \w     84.00 121.00   1.00   15.00    --  111.00-125.00 -90.00   37
 27  \w    118.00 144.00   1.00   15.00    --  111.00 125.00  60.00   26
 28  \w    147.00 172.00   1.00   15.00    --  111.00 125.00  60.00   25
 29  \w     34.00  99.00   1.00   15.00    --  111.00 -95.00-180.00   65
 30  \w    116.00 176.00   1.00   15.00    --  111.00  30.00 120.00   60
 31  \w     86.00 112.00   1.00   15.00    --  111.00 -61.00-120.00   26
 32  \w     52.00  78.00   1.00   15.00    --  111.00 -61.00-120.00   26
 33  \w     87.00 117.00   1.00   15.00    --  111.00-125.00 120.00   30
 34  \w    149.00 175.00   1.00   15.00    --  111.00  77.00   0.00   26
 35  \w     66.00 176.00   1.00   15.00    --  111.00  15.00 -90.00  110
 36  \w    120.00 172.00   1.00   15.00    --  111.00 125.00-150.00   52
 37  \w     30.00  83.00   1.00   15.00    --  111.00 -95.00 -30.00   53
 38  \w     43.00  68.00   1.00   15.00    --  111.00 -61.00  90.00   25
 39  \w     73.00  98.00   1.00   15.00    --  111.00 -61.00  90.00   25
 40  \w     46.00  72.00   1.00   15.00    --  111.00 -61.00-180.00   26
 41  \w     56.00 110.00   1.00   15.00    --  111.00 -61.00 -30.00   54
;
_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      0.1287969000
_diffrn_orient_matrix_UB_12      -0.0227686000
_diffrn_orient_matrix_UB_13      0.0315094000
_diffrn_orient_matrix_UB_21      0.0696454000
_diffrn_orient_matrix_UB_22      -0.0233961000
_diffrn_orient_matrix_UB_23      -0.0319026000
_diffrn_orient_matrix_UB_31      0.0801749000
_diffrn_orient_matrix_UB_32      0.0527785000
_diffrn_orient_matrix_UB_33      -0.0220171000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0973
_diffrn_reflns_av_unetI/netI     0.0391
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            51748
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.000
_diffrn_reflns_theta_min         3.562
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.757
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73710
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.34b (Rigaku Oxford Diffraction, 2017)
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    1.321
_exptl_crystal_description       block
_exptl_crystal_F_000             3168
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.18
_refine_diff_density_max         1.833
_refine_diff_density_min         -2.100
_refine_diff_density_rms         0.118
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1555
_refine_ls_number_reflns         51748
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0736
_refine_ls_R_factor_gt           0.0592
_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^)+(0.1210P)^2^+3.1926P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1761
_refine_ls_wR_factor_ref         0.1893
_reflns_Friedel_coverage         0.000
_reflns_number_gt                40276
_reflns_number_total             51748
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt03358k2.cif
_cod_data_source_block           153amm18_twin
_cod_depositor_comments
'Adding full bibliography for 7701212--7701213.cif.'
_cod_database_code               7701212
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C21 H40 N O2 P2 Rh'
_shelx_estimated_absorpt_t_max   0.376
_shelx_estimated_absorpt_t_min   0.273
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5797(7)
 0.4203(7)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All Rh(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 HB-P5 \\sim HB-P6
 with sigma of 0.04
 HC-P8 \\sim HC-P7
 with sigma of 0.04
 HE-P12 \\sim HE-P11
 with sigma of 0.04
 HD-P9 \\sim HD-P10
 with sigma of 0.04
 HA-P4 \\sim P4-HA
 with sigma of 0.04
 H-P1 \\sim H-P2
 with sigma of 0.04
 HA-P4 \\sim HA-P3
 with sigma of 0.04
 Rh4-HC \\sim Rh1-H \\sim Rh2-HA \\sim Rh5-HD \\sim Rh3-HB \\sim Rh6-HE
 with sigma of 0.02
4. Restrained planarity
 Rh2, P3, P4, N2
 with sigma of 0.1
 Rh6, P11, P12, N6
 with sigma of 0.1
 Rh4, P7, P8, N4
 with sigma of 0.1
 Rh3, HB, P5, P6, N3
 with sigma of 0.1
 Rh4, HC, P7, P8, N4
 with sigma of 0.1
 Rh5, HD, P9, P10, N5
 with sigma of 0.1
 Rh6, HE, P11, P12, N6
 with sigma of 0.1
 Rh1, H, P1, P2, N1
 with sigma of 0.1
 Rh2, HA, P3, P4, N2
 with sigma of 0.1
5.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C23(H23), C24(H24), C25(H25), C44(H44), C45(H45),
 C46(H46), C64(H64), C65(H65), C66(H66), C85(H85), C86(H86), C87(H87),
 C106(H106), C107(H107), C108(H108)
5.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,
 H21B,H21C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
 C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C36(H36A,H36B,
 H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C40(H40A,H40B,H40C), C41(H41A,
 H41B,H41C), C42(H42A,H42B,H42C), C036(H03A,H03B,H03C), C49(H49A,H49B,H49C),
 C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C53(H53A,H53B,H53C), C54(H54A,H54B,
 H54C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C60(H60A,
 H60B,H60C), C61(H61A,H61B,H61C), C62(H62A,H62B,H62C), C69(H69A,H69B,H69C),
 C70(H70A,H70B,H70C), C71(H71A,H71B,H71C), C73(H73A,H73B,H73C), C74(H74A,H74B,
 H74C), C75(H75A,H75B,H75C), C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C79(H79A,
 H79B,H79C), C81(H81A,H81B,H81C), C82(H82A,H82B,H82C), C83(H83A,H83B,H83C),
 C90(H90A,H90B,H90C), C91(H91A,H91B,H91C), C92(H92A,H92B,H92C), C94(H94A,H94B,
 H94C), C95(H95A,H95B,H95C), C96(H96A,H96B,H96C), C98(H98A,H98B,H98C), C99(H99A,
 H99B,H99C), C100(H10D,H10E,H10F), C102(H10G,H10H,H10I), C103(H10J,H10K,H10L),
 C104(H10M,H10N,H10O), C111(H11A,H11B,H11C), C112(H11D,H11E,H11F), C113(H11G,
 H11H,H11I), C115(H11J,H11K,H11L), C116(H11M,H11N,H11O), C117(H11P,H11Q,H11R),
 C119(H11S,H11T,H11U), C120(H12D,H12E,H12F), C121(H12G,H12H,H12I), C123(H12J,
 H12K,H12L), C124(H12M,H12N,H12O), C125(H12P,H12Q,H12R)
;
_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 1.685
_oxdiff_exptl_absorpt_empirical_full_min 0.609
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
_twin_special_details
;
Component 2 rotated by -179.9674\% 
 around [0.00 0.45 -0.89] (reciprocal) or [-0.05 0.71 -0.71] (direct)
;