Elucidation of the resting state of a rhodium NNN-pincer hydrogenation catalyst that features a remarkably upfield hydride (1)H NMR chemical shift.
Hänninen, Mikko M; Zamora, Matthew T.; MacNeil, Connor S.; Knott, Jackson P.; Hayes, Paul G.; Chemical communications (Cambridge, England) 52 (2016) 586–589; doi:10.1039/c5cc08348f

data_7118214
_publ_section_title
;
 Elucidation of the resting state of a rhodium NNN-pincer hydrogenation
 catalyst that features a remarkably upfield hydride (1)H NMR chemical
 shift.
;
_journal_issue                   3
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              586
_journal_page_last               589
_journal_paper_doi               10.1039/c5cc08348f
_journal_volume                  52
_journal_year                    2016
_chemical_formula_moiety         'C48 H48 N3 P2 Rh'
_chemical_formula_sum            'C48 H48 N3 P2 Rh'
_chemical_formula_weight         831.74
_chemical_properties_physical    'Air-sensitive, Moisture-sensitive'
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2014-11-12
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_audit_update_record
;
2014-11-14 deposited with the CCDC.
2015-11-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 118.406(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.185(10)
_cell_length_b                   18.144(11)
_cell_length_c                   15.477(10)
_cell_measurement_reflns_used    207
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      12.01
_cell_measurement_theta_min      2.66
_cell_volume                     3998(4)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_temperature      173.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.4529
_diffrn_reflns_av_unetI/netI     0.4385
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            31351
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         1.818
_exptl_absorpt_coefficient_mu    0.545
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.5778
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.382
_exptl_crystal_description       block
_exptl_crystal_F_000             1728
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.593
_refine_diff_density_min         -0.835
_refine_diff_density_rms         0.134
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.894
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     507
_refine_ls_number_reflns         7034
_refine_ls_number_restraints     317
_refine_ls_restrained_S_all      0.879
_refine_ls_R_factor_all          0.2886
_refine_ls_R_factor_gt           0.0832
_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^)+(0.0285P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1122
_refine_ls_wR_factor_ref         0.1692
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2238
_reflns_number_total             7034
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc08348f2.cif
_cod_data_source_block           2_ph14030
_cod_database_code               7118214
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.947
_shelx_estimated_absorpt_t_min   0.947
_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
 C47-H47A = C47-H47B = C48-H48A = C48-H48B
 0.98 with sigma of 0.02
 Rh1-H47A \\sim Rh1-H47B \\sim Rh1-H48A \\sim Rh1-H48B
 with sigma of 0.02
 H47A-H47B \\sim H48A-H48B
 with sigma of 0.02
 C48-H47A \\sim C48-H47B \\sim C47-H48A \\sim C47-H48B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C38 \\sim C43 \\sim C42 \\sim C41 \\sim C40 \\sim C39 \\sim C22 \\sim C17 \\sim
C18 \\sim C19 \\sim C20 \\sim C21: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C4 \\sim C3 \\sim C2 \\sim C1: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C5 \\sim C6 \\sim
C7 \\sim C8 \\sim C9 \\sim C10 \\sim C26 \\sim C31 \\sim C30 \\sim C29 \\sim
C28 \\sim C27 \\sim C32 \\sim C37 \\sim C35 \\sim C34 \\sim C33: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N1) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(N3) \\sim
Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C26) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C25) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C44)
\\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C46) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C48) \\sim Ueq, Uanis(C47) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4.a Ternary CH refined with riding coordinates:
 C23(H23), C44(H44)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C12(H12), C13(H13),
 C14(H14), C15(H15), C16(H16), C33(H33), C34(H34), C35(H35), C36(H36), C37(H37),
  C27(H27), C28(H28), C29(H29), C30(H30), C31(H31), C18(H18), C19(H19),
 C21(H21), C22(H22), C39(H39), C40(H40), C42(H42), C43(H43)
4.c Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C24(H24A,H24B,H24C), C45(H45A,H45B,H45C), C46(H46A,H46B,
 H46C)
;