Differences in the cyclometalation reactivity of bisphosphinimine-supported organo-rare earth complexes.
Zamora, Matthew T.; Johnson, Kevin R. D.; Hänninen, Mikko M; Hayes, Paul G.; Dalton transactions (Cambridge, England : 2003) 43 (2014) 10739–10750; doi:10.1039/c4dt00863d

data_7030939
_publ_section_title
;
 Differences in the cyclometalation reactivity of
 bisphosphinimine-supported organo-rare earth complexes.
;
_journal_issue                   28
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10739
_journal_page_last               10750
_journal_paper_doi               10.1039/c4dt00863d
_journal_volume                  43
_journal_year                    2014
_chemical_formula_moiety         'C92 H87 N6 P4 Sm'
_chemical_formula_sum            'C92 H87 N6 P4 Sm'
_chemical_formula_weight         1550.90
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     heavy
_audit_creation_date             2014-03-05
_audit_creation_method
;
Olex2 1.2
(compiled 2014.02.28 svn.r2899 for OlexSys, GUI svn.r4781)
;
_cell_angle_alpha                104.3038(9)
_cell_angle_beta                 101.2213(9)
_cell_angle_gamma                95.5028(9)
_cell_formula_units_Z            2
_cell_length_a                   12.3595(11)
_cell_length_b                   13.8452(12)
_cell_length_c                   24.642(2)
_cell_measurement_reflns_used    9233
_cell_measurement_temperature    173
_cell_measurement_theta_max      25.939
_cell_measurement_theta_min      2.272
_cell_volume                     3961.7(6)
_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 0.997
_diffrn_measured_fraction_theta_max 0.997
_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  0.0905
_diffrn_reflns_av_unetI/netI     0.0724
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            56897
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         0.875
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.872
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6870
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0674 before and 0.0454 after correction.
The Ratio of minimum to maximum transmission is 0.9217.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'light red'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.300
_exptl_crystal_description       block
_exptl_crystal_F_000             1606
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.16
_refine_diff_density_max         1.579
_refine_diff_density_min         -0.581
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.993
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     993
_refine_ls_number_reflns         13911
_refine_ls_number_restraints     66
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0487
_refine_ls_R_factor_gt           0.0384
_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^)+(0.0533P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0931
_refine_ls_wR_factor_ref         0.0965
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11555
_reflns_number_total             13911
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4dt00863d1.cif
_cod_data_source_block           4_ph14006_01m
_cod_depositor_comments
'Adding full bibliography for 7030936--7030940.cif.'
_cod_original_cell_volume        3961.6(6)
_cod_database_code               7030939
_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}
{C6A, C6B}
{C7A, C7B}
{C11A, C11B}
{C14A, C14B}
{C44A, C44B}
{C85A, C85B}
3. Restrained planarity
 C5A, C6A, C7A, C8A, C9A, C10A
 with sigma of 0.05
 C5B, C6B, C7B, C8B, C9B, C10B
 with sigma of 0.05
4. Uiso/Uaniso restraints and constraints
Uanis(C75) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C77) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.005
Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.005
Uanis(C86A) \\sim Ueq, Uanis(C87A) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(C46A) \\sim Ueq, Uanis(C95) \\sim Ueq, Uanis(C96) \\sim Ueq: with sigma
of 0.001 and sigma for terminal atoms of 0.005
Uanis(C5A) = Uanis(C5B)
Uanis(C6A) = Uanis(C6B)
Uanis(C7A) = Uanis(C7B)
Uanis(C11A) = Uanis(C11B)
Uanis(C85A) = Uanis(C85B)
Uanis(C44B) = Uanis(C44A)
Uanis(C14A) = Uanis(C14B)
5. Others
 Sof(C11B)=Sof(C12B)=Sof(H12B)=Sof(C13B)=Sof(H13B)=Sof(C14B)=Sof(H14B)=
 Sof(C15B)=Sof(H15B)=Sof(C16B)=Sof(H16B)=1-FVAR(1)
 Sof(C11A)=Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(H13A)=Sof(C14A)=Sof(H14A)=
 Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(H16A)=FVAR(1)
 Sof(C8B)=Sof(H8B)=Sof(C5B)=Sof(C6B)=Sof(H6B)=Sof(C7B)=Sof(H7B)=Sof(C9B)=
 Sof(H9B)=Sof(C10B)=Sof(H10B)=1-FVAR(2)
 Sof(C5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=
 Sof(H10A)=Sof(C8A)=Sof(H8A)=FVAR(2)
 Sof(C85B)=Sof(H85B)=Sof(C86B)=Sof(H86D)=Sof(H86E)=Sof(H86F)=Sof(C87B)=
 Sof(H87D)=Sof(H87E)=Sof(H87F)=1-FVAR(3)
 Sof(C85A)=Sof(H85A)=Sof(C86A)=Sof(H86A)=Sof(H86B)=Sof(H86C)=Sof(C87A)=
 Sof(H87A)=Sof(H87B)=Sof(H87C)=FVAR(3)
 Sof(C46B)=Sof(H46D)=Sof(H46E)=Sof(H46F)=Sof(C45B)=Sof(H45D)=Sof(H45E)=
 Sof(H45F)=Sof(C44B)=Sof(H44B)=1-FVAR(4)
 Sof(C46A)=Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(C44A)=Sof(H44A)=Sof(C45A)=
 Sof(H45A)=Sof(H45B)=Sof(H45C)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C35(H35), C85A(H85A), C94(H94), C85B(H85B), C44A(H44A), C44B(H44B)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C24(H24),
 C25(H25), C26(H26), C27(H27), C28(H28), C30(H30), C31(H31), C33(H33), C39(H39),
  C40(H40), C42(H42), C43(H43), C52(H52), C53(H53), C56(H56), C57(H57),
 C58(H58), C59(H59), C60(H60), C62(H62), C63(H63), C64(H64), C65(H65), C66(H66),
  C68(H68), C69(H69), C70(H70), C71(H71), C72(H72), C74(H74), C75(H75),
 C76(H76), C77(H77), C78(H78), C80(H80), C81(H81), C83(H83), C84(H84), C89(H89),
  C90(H90), C92(H92), C93(H93), C12A(H12A), C13A(H13A), C14A(H14A), C15A(H15A),
 C16A(H16A), C12B(H12B), C13B(H13B), C14B(H14B), C15B(H15B), C16B(H16B),
 C6A(H6A), C7A(H7A), C8B(H8B), C9A(H9A), C10A(H10A), C6B(H6B), C7B(H7B),
 C8A(H8A), C9B(H9B), C10B(H10B)
6.c Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C46A(H46A,H46B,H46C), C95(H95A,H95B,
 H95C), C96(H96A,H96B,H96C), C86A(H86A,H86B,H86C), C87A(H87A,H87B,H87C),
 C86B(H86D,H86E,H86F), C87B(H87D,H87E,H87F), C45A(H45A,H45B,H45C), C46B(H46D,
 H46E,H46F), C45B(H45D,H45E,H45F)
;