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_7118216
_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         'C92 H90 N6 P4 Rh2, C6 H6'
_chemical_formula_sum            'C98 H96 N6 P4 Rh2'
_chemical_formula_weight         1687.50
_chemical_properties_physical    'Air-sensitive, Moisture-sensitive'
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-10-14
_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                 119.527(5)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   42.986(11)
_cell_length_b                   17.237(4)
_cell_length_c                   27.577(9)
_cell_measurement_reflns_used    9302
_cell_measurement_temperature    173
_cell_measurement_theta_max      25.520
_cell_measurement_theta_min      2.343
_cell_volume                     17779(8)
_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
_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  0.0767
_diffrn_reflns_av_unetI/netI     0.0551
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       51
_diffrn_reflns_limit_h_min       -51
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            105476
_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         25.000
_diffrn_reflns_theta_min         1.498
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.492
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6662
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0792 before and 0.0726 after correction.
The Ratio of minimum to maximum transmission is 0.8937.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.261
_exptl_crystal_description       block
_exptl_crystal_F_000             7008
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.848
_refine_diff_density_min         -0.634
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1139
_refine_ls_number_reflns         15648
_refine_ls_number_restraints     353
_refine_ls_restrained_S_all      1.134
_refine_ls_R_factor_all          0.0609
_refine_ls_R_factor_gt           0.0412
_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^)+(0.0599P)^2^+19.8721P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1085
_refine_ls_wR_factor_ref         0.1168
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12225
_reflns_number_total             15648
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc08348f2.cif
_cod_data_source_block           4_ph14013_0m
_cod_original_cell_volume        17779(9)
_cod_database_code               7118216
_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
{C5A, C5B, C5C}
{C8A, C8B, C8C}
3. Restrained distances
 C23A-C24A = C25A-C23A
 1.54 with sigma of 0.01
 C6A-C5A = C7A-C6A = C8A-C7A = C9A-C8A = C9A-C10A = C5A-C10A
 1.39 with sigma of 0.01
 C6B-C5B = C7B-C6B = C8B-C7B = C9B-C8B = C9B-C10B = C5B-C10B
 1.39 with sigma of 0.01
 C6C-C5C = C7C-C6C = C8C-C7C = C9C-C8C = C9C-C10C = C5C-C10C
 1.39 with sigma of 0.01
 C4S-C9S = C5S-C4S = C5S-C6S = C6S-C7S = C7S-C8S = C9S-C8S
 1.39 with sigma of 0.005
 N6-H6
 0.9 with sigma of 0.01
 C24A-C25A
 2.9 with sigma of 0.04
4. Restrained planarity
 C5A, C10A, C9A, C8A, C7A, C6A
 with sigma of 0.1
 C5B, C10B, C9B, C8B, C7B, C6B
 with sigma of 0.1
 C5C, C10C, C9C, C8C, C7C, C6C
 with sigma of 0.1
 C4S, C5S, C6S, C7S, C8S, C9S
 with sigma of 0.1
5. Rigid bond restraints
 C17, C18, C19, C20, C21, C22
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C9B, C6A, C7A, C8B, C8C, C6B, C7B, C9C, C8A, C10A, C9A, C7C, C6C, C10B, C10C,
 C5A, C5C, C5B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Uiso/Uaniso restraints and constraints
C7S \\sim C5S \\sim C4S \\sim C9S \\sim C8S \\sim C6S: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.04
C6S \\sim C5S \\sim C4S \\sim C9S \\sim C8S \\sim C7S: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C20)
\\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq: with sigma of 0.003 and
sigma for terminal atoms of 0.006
Uanis(C94) \\sim Ueq, Uanis(C95) \\sim Ueq, Uanis(C96) \\sim Ueq: with sigma of
0.003 and sigma for terminal atoms of 0.006
Uanis(C75) \\sim Ueq, Uanis(C74) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.006
Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(C23B) \\sim Ueq, Uanis(C25B) \\sim Ueq, Uanis(C25A) \\sim Ueq,
Uanis(C24B) \\sim Ueq, Uanis(C23A) \\sim Ueq, Uanis(C24A) \\sim Ueq: with sigma
of 0.007 and sigma for terminal atoms of 0.014
Uanis(C5A) \\sim Ueq, Uanis(C9B) \\sim Ueq, Uanis(C6A) \\sim Ueq, Uanis(C5C)
\\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C8B) \\sim Ueq, Uanis(C8C) \\sim Ueq,
Uanis(C6B) \\sim Ueq, Uanis(C9C) \\sim Ueq, Uanis(C5B) \\sim Ueq, Uanis(C8A)
\\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(C9A) \\sim Ueq, Uanis(C7C) \\sim Ueq,
Uanis(C6C) \\sim Ueq, Uanis(C10B) \\sim Ueq, Uanis(C10C) \\sim Ueq, Uanis(C7B)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C5A) = Uanis(C5B) = Uanis(C5C)
Uanis(C8A) = Uanis(C8B) = Uanis(C8C)
7. Others
 1*[Sof(C5A)+Sof(C6A)+Sof(H6A)+Sof(C7A)+Sof(H7A)+Sof(C8A)+Sof(H8A)+Sof(C10A)+
 Sof(H10A)+Sof(C9A)+Sof(H9A)]+1*[Sof(C9B)+Sof(H9B)+Sof(C8B)+Sof(H8B)+Sof(C6B)+
 Sof(H6B)+Sof(C7B)+Sof(H7B)+Sof(C5B)+Sof(C10B)+Sof(H10B)]+1*[Sof(C5C)+Sof(C8C)+
 Sof(H8C)+Sof(C9C)+Sof(H9C)+Sof(C7C)+Sof(H7C)+Sof(C6C)+Sof(H6C)+Sof(C10C)+
 Sof(H10C)]=1 with esd of 0.0001
 Sof(C24B)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C25B)=Sof(H25D)=Sof(H25E)=
 Sof(H25F)=Sof(C23B)=Sof(H23B)=1-FVAR(1)
 Sof(C23A)=Sof(H23A)=Sof(C25A)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C24A)=
 Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(1)
 Sof(C5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8A)=Sof(C10A)=
 Sof(H10A)=Sof(C9A)=Sof(H9A)=FVAR(2)
 Sof(C9B)=Sof(H9B)=Sof(C8B)=Sof(H8B)=Sof(C6B)=Sof(H6B)=Sof(C7B)=Sof(H7B)=
 Sof(C5B)=Sof(C10B)=Sof(H10B)=FVAR(3)
 Sof(C5C)=Sof(C8C)=Sof(H8C)=Sof(C9C)=Sof(H9C)=Sof(C7C)=Sof(H7C)=Sof(C6C)=
 Sof(H6C)=Sof(C10C)=Sof(H10C)=FVAR(4)
 Fixed Sof: C8S(0.5) H8S(0.5) C7S(0.5) H7S(0.5) C6S(0.5) H6S(0.5) C9S(0.5)
 H9S(0.5) C4S(0.5) H4S(0.5) C5S(0.5) H5S(0.5)
8.a Ternary CH refined with riding coordinates:
 C73(H73), C44(H44), C95(H95), C23A(H23A), C23B(H23B)
8.b Aromatic/amide H refined with riding coordinates:
 C86(H86), C53(H53), C56(H56), C39(H39), C87(H87), C27(H27), C77(H77),
 C83(H83), C68(H68), C3(H3), C62(H62), C85(H85), C40(H40), C22(H22), C15(H15),
 C31(H31), C58(H58), C43(H43), C42(H42), C33(H33), C72(H72), C60(H60), C52(H52),
  C78(H78), C57(H57), C89(H89), C71(H71), C28(H28), C37(H37), C30(H30), C2(H2),
 C18(H18), C79(H79), C81(H81), C12(H12), C80(H80), C69(H69), C66(H66), C35(H35),
  C29(H29), C84(H84), C36(H36), C21(H21), C63(H63), C65(H65), C59(H59),
 C34(H34), C19(H19), C13(H13), C16(H16), C93(H93), C64(H64), C92(H92), C90(H90),
  C14(H14), C9B(H9B), C6A(H6A), C7A(H7A), C8B(H8B), C2S(H2S), C1S(H1S),
 C3S(H3S), C8S(H8S), C7S(H7S), C6S(H6S), C9S(H9S), C4S(H4S), C5S(H5S), C8C(H8C),
  C6B(H6B), C7B(H7B), C9C(H9C), C8A(H8A), C10A(H10A), C9A(H9A), C7C(H7C),
 C6C(H6C), C10B(H10B), C10C(H10C)
8.c Idealised Me refined as rotating group:
 C74(H74A,H74B,H74C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C75(H75A,H75B,
 H75C), C94(H94A,H94B,H94C), C96(H96A,H96B,H96C), C25A(H25A,H25B,H25C),
 C24A(H24A,H24B,H24C), C24B(H24D,H24E,H24F), C25B(H25D,H25E,H25F)
;