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_7118213
_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         'C54 H58 N3 P2 Rh'
_chemical_formula_sum            'C54 H58 N3 P2 Rh'
_chemical_formula_weight         913.88
_chemical_name_systematic
;
 ?
;
_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             2014-04-11
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_audit_update_record
;
2014-11-14 deposited with the CCDC.
2015-11-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 111.548(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.580(3)
_cell_length_b                   21.768(6)
_cell_length_c                   17.290(4)
_cell_measurement_reflns_used    9961
_cell_measurement_temperature    173
_cell_measurement_theta_max      26.910
_cell_measurement_theta_min      2.257
_cell_volume                     4754(2)
_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  0.0617
_diffrn_reflns_av_unetI/netI     0.0401
_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       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            59111
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.000
_diffrn_reflns_theta_min         1.574
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.465
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6603
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0884 before and 0.0720 after correction.
The Ratio of minimum to maximum transmission is 0.8855.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'dark orange'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.277
_exptl_crystal_description       plate
_exptl_crystal_F_000             1912
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.458
_refine_diff_density_min         -0.415
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     639
_refine_ls_number_reflns         9342
_refine_ls_number_restraints     180
_refine_ls_restrained_S_all      1.119
_refine_ls_R_factor_all          0.0457
_refine_ls_R_factor_gt           0.0331
_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^)+(0.0222P)^2^+5.5056P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0754
_refine_ls_wR_factor_ref         0.0823
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7766
_reflns_number_total             9342
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc08348f2.cif
_cod_data_source_block           1_ph14010_0m
_cod_database_code               7118213
_shelxl_version_number           2013-4
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{C53A, C53B}
{C56A, C56B}
{C38A, C38B}
3. Uiso/Uaniso restraints and constraints
C38A \\sim C43B \\sim C42B \\sim C41B \\sim C40B \\sim C39B: within 2A with
sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(C45A) \\sim Ueq, Uanis(C46B) \\sim Ueq, Uanis(C45B) \\sim Ueq,
Uanis(C46A) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C36)
\\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C7) \\sim Ueq: with
sigma of 0.004 and sigma for terminal atoms of 0.008
Uanis(C28) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30) \\sim Ueq: with sigma of
0.004 and sigma for terminal atoms of 0.008
Uanis(C53A) \\sim Ueq, Uanis(C53B) \\sim Ueq, Uanis(C56A) \\sim Ueq,
Uanis(C56B) \\sim Ueq, Uanis(C55A) \\sim Ueq, Uanis(C55B) \\sim Ueq,
Uanis(C54B) \\sim Ueq, Uanis(C54A) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C24) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C25) \\sim Ueq: with sigma of
0.002 and sigma for terminal atoms of 0.004
Uanis(C53A) = Uanis(C53B)
Uanis(C56A) = Uanis(C56B)
Uanis(C38A) = Uanis(C38B)
4. Others
 Sof(H57C)=Sof(H57D)=Sof(H52C)=Sof(H52D)=Sof(C55B)=Sof(H55C)=Sof(H55D)=
 Sof(C54B)=Sof(H54C)=Sof(H54D)=Sof(C53B)=Sof(H53C)=Sof(H53D)=Sof(C56B)=
 Sof(H56C)=Sof(H56D)=1-FVAR(1)
 Sof(H57A)=Sof(H57B)=Sof(C56A)=Sof(H56A)=Sof(H56B)=Sof(H52A)=Sof(H52B)=
 Sof(C53A)=Sof(H53A)=Sof(H53B)=Sof(C54A)=Sof(H54A)=Sof(H54B)=Sof(C55A)=
 Sof(H55A)=Sof(H55B)=FVAR(1)
 Sof(C43B)=Sof(H43B)=Sof(C44B)=Sof(H44B)=Sof(C41B)=Sof(C42B)=Sof(H42B)=
 Sof(C40B)=Sof(H40B)=Sof(C38B)=Sof(C39B)=Sof(H39B)=Sof(C46B)=Sof(H46D)=
 Sof(H46E)=Sof(H46F)=Sof(C45B)=Sof(H45D)=Sof(H45E)=Sof(H45F)=1-FVAR(2)
 Sof(C39A)=Sof(H39A)=Sof(C41A)=Sof(C38A)=Sof(C40A)=Sof(H40A)=Sof(C42A)=
 Sof(H42A)=Sof(C45A)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(C44A)=Sof(H44A)=
 Sof(C46A)=Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(C43A)=Sof(H43A)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C51(H51), C50(H50), C23(H23), C44A(H44A), C44B(H44B)
5.b Secondary CH2 refined with riding coordinates:
 C57(H57A,H57B), C57(H57C,H57D), C56A(H56A,H56B), C52(H52A,H52B), C52(H52C,
 H52D), C53A(H53A,H53B), C54A(H54A,H54B), C55A(H55A,H55B), C55B(H55C,H55D),
 C54B(H54C,H54D), C53B(H53C,H53D), C56B(H56C,H56D)
5.c Aromatic/amide H refined with riding coordinates:
 C22(H22), C19(H19), C37(H37), C16(H16), C12(H12), C15(H15), C3(H3), C13(H13),
 C2(H2), C21(H21), C30(H30), C39A(H39A), C27(H27), C33(H33), C36(H36), C6(H6),
 C8(H8), C14(H14), C9(H9), C18(H18), C10(H10), C28(H28), C31(H31), C35(H35),
 C43B(H43B), C29(H29), C40A(H40A), C42A(H42A), C34(H34), C7(H7), C42B(H42B),
 C40B(H40B), C39B(H39B), C43A(H43A)
5.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C45A(H45A,H45B,H45C), C46A(H46A,
 H46B,H46C), C46B(H46D,H46E,H46F), C45B(H45D,H45E,H45F)
;