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_7118215
_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 H54 N3 P2 Rh, 2(C6 H6)'
_chemical_formula_sum            'C72 H66 N3 P2 Rh'
_chemical_formula_weight         1138.12
_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
_audit_creation_date             2014-09-19
_audit_creation_method
;
Olex2 1.2
(compiled 2014.08.28 svn.r2986 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                 109.213(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.567(4)
_cell_length_b                   28.198(8)
_cell_length_c                   16.293(5)
_cell_measurement_reflns_used    9916
_cell_measurement_temperature    173
_cell_measurement_theta_max      24.63
_cell_measurement_theta_min      2.23
_cell_volume                     5886(3)
_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)'
_diffrn_ambient_temperature      173
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.0700
_diffrn_reflns_av_unetI/netI     0.0609
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            74858
_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         1.444
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.390
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6879
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0637 before and 0.0560 after correction.
The Ratio of minimum to maximum transmission is 0.9226.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.284
_exptl_crystal_description       plate
_exptl_crystal_F_000             2376
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.932
_refine_diff_density_min         -1.055
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.119
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     725
_refine_ls_number_reflns         10367
_refine_ls_number_restraints     282
_refine_ls_restrained_S_all      1.148
_refine_ls_R_factor_all          0.0828
_refine_ls_R_factor_gt           0.0619
_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^)+(0.0506P)^2^+22.9074P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1491
_refine_ls_wR_factor_ref         0.1601
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8150
_reflns_number_total             10367
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc08348f2.cif
_cod_data_source_block           3_ph14024_c_0m
_cod_database_code               7118215
_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}
{C46A, C46B}
3. Restrained distances
 C24B-C23B = C25B-C23B = C25A-C23A = C24A-C23A
 1.55 with sigma of 0.005
 C23A-C20 = C23B-C20
 1.54 with sigma of 0.005
4. Restrained planarity
 C10S, C7S, C12S, C8S, H8S, C9S, H9S, H7S, H10S, C11S, H12S, H11S
 with sigma of 0.1
 C2S, C6S, H6S, C5S, C1S, C4S, H5S, H1S, H4S, C3S, H2S, H3S
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
C1S \\sim C6S \\sim C5S \\sim C4S \\sim C3S \\sim C2S: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
C11S \\sim C10S \\sim C9S \\sim C8S \\sim C7S \\sim C12S: 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 \\sim C49 \\sim C53 \\sim
C54 \\sim C52 \\sim C51 \\sim C50: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C25B \\sim C24B \\sim C24A \\sim C25A: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01
C23B \\sim C23A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
Uanis(C46B) \\sim Ueq, Uanis(C46A) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C57)
\\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C59) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(C25A) \\sim Ueq, Uanis(C24A) \\sim Ueq, Uanis(C45A) \\sim Ueq,
Uanis(C45B) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C23A) \\sim Ueq, Uanis(C23B) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C25B) \\sim Ueq, Uanis(C25A) \\sim Ueq, Uanis(C24B) \\sim Ueq,
Uanis(C24A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C44A) = Uanis(C44B)
Uanis(C46A) = Uanis(C46B)
6. Others
 Sof(C45B)=Sof(H45D)=Sof(H45E)=Sof(H45F)=Sof(C44B)=Sof(H44B)=Sof(C46B)=
 Sof(H46D)=Sof(H46E)=Sof(H46F)=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(C24B)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C25B)=Sof(H25D)=Sof(H25E)=
 Sof(H25F)=Sof(C23B)=Sof(H23B)=1-FVAR(2)
 Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25A)=
 Sof(H25A)=Sof(H25B)=Sof(H25C)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C23A(H23A), C44A(H44A), C44B(H44B), C23B(H23B)
7.b Aromatic/amide H refined with riding coordinates:
 C28(H28), C10(H10), C2(H2), C39(H39), C31(H31), C18(H18), C43(H43), C16(H16),
 C22(H22), C27(H27), C37(H37), C33(H33), C6(H6), C7(H7), C30(H30), C12(H12),
 C14(H14), C42(H42), C9(H9), C8(H8), C21(H21), C50(H50), C35(H35), C13(H13),
 C29(H29), C34(H34), C40(H40), C19(H19), C56(H56), C3(H3), C60(H60), C59(H59),
 C15(H15), C36(H36), C54(H54), C51(H51), C58(H58), C52(H52), C53(H53), C57(H57),
  C2S(H2S), C3S(H3S), C4S(H4S), C5S(H5S), C6S(H6S), C1S(H1S), C10S(H10S),
 C11S(H11S), C12S(H12S), C7S(H7S), C8S(H8S), C9S(H9S)
7.c Fitted hexagon refined as free rotating group:
 C2S(C3S,C4S,C5S,C6S,C1S), C10S(C11S,C12S,C7S,C8S,C9S)
7.d Idealised Me refined as rotating group:
 C46A(H46A,H46B,H46C), C45A(H45A,H45B,H45C), C24A(H24A,H24B,H24C), C25A(H25A,
 H25B,H25C), C45B(H45D,H45E,H45F), C46B(H46D,H46E,H46F), C24B(H24D,H24E,H24F),
 C25B(H25D,H25E,H25F)
;