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_7030936
_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         'C54 H66 N3 P2 Si2 Y'
_chemical_formula_sum            'C54 H66 N3 P2 Si2 Y'
_chemical_formula_weight         964.12
_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     direct
_audit_creation_date             2014-03-03
_audit_creation_method
;
Olex2 1.2
(compiled 2014.02.28 svn.r2899 for OlexSys, GUI svn.r4781)
;
_cell_angle_alpha                84.8276(9)
_cell_angle_beta                 78.9662(9)
_cell_angle_gamma                69.6098(9)
_cell_formula_units_Z            2
_cell_length_a                   9.7370(7)
_cell_length_b                   12.1842(9)
_cell_length_c                   24.1371(18)
_cell_measurement_reflns_used    9912
_cell_measurement_temperature    173
_cell_measurement_theta_max      28.477
_cell_measurement_theta_min      2.361
_cell_volume                     2633.7(3)
_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 0.998
_diffrn_measured_fraction_theta_max 0.998
_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  0.0208
_diffrn_reflns_av_unetI/netI     0.0238
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            25832
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.720
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.250
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.5763
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0806 before and 0.0309 after correction.
The Ratio of minimum to maximum transmission is 0.7727.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.216
_exptl_crystal_description       needle
_exptl_crystal_F_000             1016
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.786
_refine_diff_density_min         -0.513
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     590
_refine_ls_number_reflns         9252
_refine_ls_number_restraints     142
_refine_ls_restrained_S_all      1.136
_refine_ls_R_factor_all          0.0460
_refine_ls_R_factor_gt           0.0403
_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^)+(0.0485P)^2^+2.8591P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0999
_refine_ls_wR_factor_ref         0.1031
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8315
_reflns_number_total             9252
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4dt00863d1.cif
_cod_data_source_block           1_ph13003_0m
_cod_depositor_comments
'Adding full bibliography for 7030936--7030940.cif.'
_cod_database_code               7030936
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{C45A, C45B}
3. Restrained distances
 C33-C32 = C34-C33 = C35-C34 = C36-C35
 1.39 with sigma of 0.005
4. Uiso/Uaniso restraints and constraints
C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.04
Uanis(C39) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42)
\\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C24) \\sim Ueq,
Uanis(C23) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.01
Uanis(C30) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C27)
\\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.01
Uanis(C44A) \\sim Ueq, Uanis(C46B) \\sim Ueq, Uanis(C44B) \\sim Ueq,
Uanis(C46A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C50) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.01
Uanis(C45A) = Uanis(C45B)
5. Others
 Sof(C44B)=Sof(H44B)=Sof(C45B)=Sof(H45D)=Sof(H45E)=Sof(H45F)=Sof(C46B)=
 Sof(H46D)=Sof(H46E)=Sof(H46F)=1-FVAR(1)
 Sof(C44A)=Sof(H44A)=Sof(C45A)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(C46A)=
 Sof(H46A)=Sof(H46B)=Sof(H46C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C23(H23), C44A(H44A), C44B(H44B)
6.b Secondary CH2 refined with riding coordinates:
 C47(H47A,H47B), C51(H51A,H51B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C12(H12), C13(H13),
 C14(H14), C15(H15), C16(H16), C18(H18), C19(H19), C21(H21), C22(H22), C27(H27),
  C28(H28), C29(H29), C30(H30), C31(H31), C33(H33), C34(H34), C35(H35),
 C36(H36), C37(H37), C39(H39), C40(H40), C42(H42), C43(H43)
6.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C48(H48A,H48B,H48C), C49(H49A,H49B,
 H49C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C),
 C45A(H45A,H45B,H45C), C46A(H46A,H46B,H46C), C50(H50A,H50B,H50C), C45B(H45D,
 H45E,H45F), C46B(H46D,H46E,H46F)
;