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_7118217
_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         'C60 H56 N3 P2 Rh'
_chemical_formula_sum            'C60 H56 N3 P2 Rh'
_chemical_formula_weight         983.92
_chemical_properties_physical    'Air-sensitive, Moisture-sensitive'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-09-24
_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                 112.133(11)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.907(7)
_cell_length_b                   27.103(13)
_cell_length_c                   16.593(9)
_cell_measurement_reflns_used    2706
_cell_measurement_temperature    173
_cell_measurement_theta_max      18.998
_cell_measurement_theta_min      2.189
_cell_volume                     5793(5)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      173.0
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1280
_diffrn_reflns_av_unetI/netI     0.2171
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            34510
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         1.503
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.386
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5650
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0672 before and 0.0563 after correction.
The Ratio of minimum to maximum transmission is 0.7580.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.128
_exptl_crystal_description       plate
_exptl_crystal_F_000             2048
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.525
_refine_diff_density_min         -1.094
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.896
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     632
_refine_ls_number_reflns         10077
_refine_ls_number_restraints     215
_refine_ls_restrained_S_all      0.902
_refine_ls_R_factor_all          0.1645
_refine_ls_R_factor_gt           0.0658
_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^)+(0.0727P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1357
_refine_ls_wR_factor_ref         0.1579
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4621
_reflns_number_total             10077
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc08348f2.cif
_cod_data_source_block           5_ph14023_0m
_cod_database_code               7118217
_shelxl_version_number           2013-4
_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. Shared sites
{C44A, C44B}
3. Restrained distances
 C44B-C45B
 1.54 with sigma of 0.02
 C46A-C44A = C46B-C44B = C45A-C44A = C45B-C44B
 1.5 with sigma of 0.01
 C24A-C23A = C25A-C23A = C24B-C23B
 1.5 with sigma of 0.01
 C25B-C23B
 1.5 with sigma of 0.01
 C25B-C24B
 2.5 with sigma of 0.02
 C25A-C24A
 2.5 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C49 \\sim C54 \\sim C53 \\sim C52 \\sim C51 \\sim C50: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
C2 \\sim C1 \\sim N1 \\sim C4 \\sim C3: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(C46A) \\sim Ueq, Uanis(C45A) \\sim Ueq, Uanis(C23A) \\sim Ueq,
Uanis(C23B) \\sim Ueq, Uanis(C45B) \\sim Ueq, Uanis(C46B) \\sim Ueq: with sigma
of 0.006 and sigma for terminal atoms of 0.012
Uanis(C24A) \\sim Ueq, Uanis(C24B) \\sim Ueq, Uanis(C25B) \\sim Ueq,
Uanis(C25A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C19) \\sim Ueq, Uanis(C20) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C1) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C3) \\sim
Ueq, Uanis(C2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of
0.02
Uanis(C44A) = Uanis(C44B)
Uanis(C24B) = Uanis(C24A)
Uanis(C25A) = Uanis(C25B)
Uanis(C24B) = Uanis(C24A)
Uanis(C25A) = Uanis(C25B)
Uanis(C23A) = Uanis(C23B)
5. Others
 Sof(C46B)=Sof(H46D)=Sof(H46E)=Sof(H46F)=Sof(C45B)=Sof(H45D)=Sof(H45E)=
 Sof(H45F)=Sof(C44B)=Sof(H44B)=1-FVAR(1)
 Sof(C44A)=Sof(H44A)=Sof(C46A)=Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(C45A)=
 Sof(H45A)=Sof(H45B)=Sof(H45C)=FVAR(1)
 Sof(C23B)=Sof(H23B)=Sof(C24B)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C25B)=
 Sof(H25D)=Sof(H25E)=Sof(H25F)=1-FVAR(2)
 Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25A)=Sof(H25A)=Sof(H25B)=
 Sof(H25C)=Sof(C23A)=Sof(H23A)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C48(H48), C47(H47), C44A(H44A), C44B(H44B), C23A(H23A), C23B(H23B)
6.b Aromatic/amide H refined with riding coordinates:
 C27(H27), C36(H36), C10(H10), C30(H30), C13(H13), C3(H3), C34(H34), C12(H12),
 C31(H31), C39(H39), C18(H18), C8(H8), C16(H16), C15(H15), C9(H9), C22(H22),
 C6(H6), C56(H56), C33(H33), C35(H35), C14(H14), C2(H2), C29(H29), C60(H60),
 C51(H51), C53(H53), C37(H37), C50(H50), C42(H42), C43(H43), C58(H58), C7(H7),
 C57(H57), C59(H59), C52(H52), C40(H40), C28(H28), C54(H54), C19(H19), C21(H21)
6.c Idealised Me refined as rotating group:
 C24A(H24A,H24B,H24C), C25A(H25A,H25B,H25C), C46A(H46A,H46B,H46C), C45A(H45A,
 H45B,H45C), C46B(H46D,H46E,H46F), C45B(H45D,H45E,H45F), C24B(H24D,H24E,H24F),
 C25B(H25D,H25E,H25F)
;