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_7030940
_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 H88 Lu N6 P4, C24 B F20'
_chemical_formula_sum            'C116 H88 B F20 Lu N6 P4'
_chemical_formula_weight         2255.58
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-03-06
_audit_creation_method
;
Olex2 1.2
(compiled 2014.02.28 svn.r2899 for OlexSys, GUI svn.r4781)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.649(5)
_cell_length_b                   22.032(5)
_cell_length_c                   45.231(10)
_cell_measurement_reflns_used    9801
_cell_measurement_temperature    173
_cell_measurement_theta_max      26.334
_cell_measurement_theta_min      2.261
_cell_volume                     21574(8)
_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  0.0524
_diffrn_reflns_av_unetI/netI     0.0226
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       56
_diffrn_reflns_limit_l_min       -56
_diffrn_reflns_number            295374
_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         25.999
_diffrn_reflns_theta_min         1.597
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.060
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6890
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0661 before and 0.0494 after correction.
The Ratio of minimum to maximum transmission is 0.9243.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.389
_exptl_crystal_description       prsim
_exptl_crystal_F_000             9136
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.428
_refine_diff_density_min         -0.380
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1371
_refine_ls_number_reflns         21194
_refine_ls_number_restraints     51
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.0406
_refine_ls_R_factor_gt           0.0285
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0274P)^2^+23.4200P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0646
_refine_ls_wR_factor_ref         0.0686
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17241
_reflns_number_total             21194
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4dt00863d1.cif
_cod_data_source_block           5_ph12017_0m
_cod_depositor_comments
'Adding full bibliography for 7030936--7030940.cif.'
_cod_database_code               7030940
_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. Restrained distances
 C71-C70 = C70-C69 = C72-C67
 1.39 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(C37) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C46B) \\sim Ueq, Uanis(C44B)
\\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C45B) \\sim Ueq:
with sigma of 0.005 and sigma for terminal atoms of 0.005
Uanis(C96) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.005
4. Others
 Sof(C46B)=Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(C44B)=Sof(H44B)=Sof(C45B)=
 Sof(H45D)=Sof(H45E)=Sof(H45F)=1-FVAR(1)
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(C44)=Sof(H44)=Sof(C46)=Sof(H46D)=
 Sof(H46E)=Sof(H46F)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C85(H85), C35(H35), C44B(H44B), C44(H44), C94(H94)
5.b Aromatic/amide H refined with riding coordinates:
 C89(H89), C18(H18), C43(H43), C80(H80), C2(H2), C81(H81), C28(H28), C66(H66),
 C93(H93), C3(H3), C30(H30), C40(H40), C72(H72), C56(H56), C27(H27), C76(H76),
 C19(H19), C83(H83), C57(H57), C90(H90), C39(H39), C84(H84), C26(H26), C21(H21),
  C24(H24), C31(H31), C22(H22), C60(H60), C64(H64), C77(H77), C63(H63),
 C42(H42), C62(H62), C12(H12), C25(H25), C6(H6), C53(H53), C52(H52), C70(H70),
 C65(H65), C71(H71), C68(H68), C78(H78), C92(H92), C8(H8), C7(H7), C14(H14),
 C9(H9), C10(H10), C16(H16), C74(H74), C58(H58), C69(H69), C75(H75), C13(H13),
 C59(H59), C20(H20), C34(H34), C33(H33), C15(H15)
5.c Idealised Me refined as rotating group:
 C86(H86A,H86B,H86C), C87(H87A,H87B,H87C), C45(H45A,H45B,H45C), C46B(H46A,H46B,
 H46C), C37(H37A,H37B,H37C), C36(H36A,H36B,H36C), C46(H46D,H46E,H46F),
 C45B(H45D,H45E,H45F), C95(H95A,H95B,H95C), C96(H96A,H96B,H96C)
;