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_7030937
_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         'C58 H70 N3 O2 P2 Si Sm'
_chemical_formula_sum            'C58 H70 N3 O2 P2 Si Sm'
_chemical_formula_weight         1081.55
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2014-02-26
_audit_creation_method
;
Olex2 1.2
(compiled 2014.02.17 svn.r2891 for OlexSys, GUI svn.r4779)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.2626(18)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.806(2)
_cell_length_b                   14.713(2)
_cell_length_c                   29.208(5)
_cell_measurement_reflns_used    9795
_cell_measurement_temperature    173
_cell_measurement_theta_max      26.526
_cell_measurement_theta_min      2.264
_cell_volume                     6240.2(16)
_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      173.0
_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  0.0434
_diffrn_reflns_av_unetI/netI     0.0367
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            72436
_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         1.556
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.049
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6194
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0733 before and 0.0605 after correction.
The Ratio of minimum to maximum transmission is 0.8310.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.151
_exptl_crystal_description       block
_exptl_crystal_F_000             2244
_exptl_crystal_size_max          0.43
_exptl_crystal_size_mid          0.325
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.431
_refine_diff_density_min         -3.086
_refine_diff_density_rms         0.130
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.200
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     719
_refine_ls_number_reflns         10985
_refine_ls_number_restraints     237
_refine_ls_restrained_S_all      1.202
_refine_ls_R_factor_all          0.0899
_refine_ls_R_factor_gt           0.0788
_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^)+(0.0209P)^2^+70.7577P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1761
_refine_ls_wR_factor_ref         0.1798
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9375
_reflns_number_total             10985
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4dt00863d1.cif
_cod_data_source_block           2_ph12044_0m
_cod_depositor_comments
'Adding full bibliography for 7030936--7030940.cif.'
_cod_original_cell_volume        6240.0(18)
_cod_database_code               7030937
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C46B-C44B
 1.45 with sigma of 0.02
 C46-C44
 1.45 with sigma of 0.02
 C45B-C44B
 1.45 with sigma of 0.02
 C45-C44
 1.45 with sigma of 0.02
 C36A-C35
 1.45 with sigma of 0.02
 C45B-C46B
 2.5 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C38B \\sim C39B \\sim C40B \\sim C41B \\sim C42B \\sim C43B: within 1.7A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C51B \\sim C52B \\sim C53B \\sim C54B: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
C51 \\sim C52 \\sim C53 \\sim C54: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08
Uanis(C37) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C25)
\\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C53) \\sim Ueq:
with sigma of 0.005 and sigma for terminal atoms of 0.02
Uanis(C38) \\sim Ueq, Uanis(C38B) \\sim Ueq, Uanis(C40B) \\sim Ueq, Uanis(C37)
\\sim Ueq, Uanis(C36A) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C57) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C49) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C57)
\\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C54) \\sim Ueq,
Uanis(C55) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C24)
\\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.02
4. Others
 Sof(C38B)=Sof(C39B)=Sof(H39B)=Sof(C40B)=Sof(H40B)=Sof(C41B)=Sof(C42B)=
 Sof(H42B)=Sof(C43B)=Sof(H43B)=Sof(C44B)=Sof(H44B)=Sof(C45B)=Sof(H45D)=
 Sof(H45E)=Sof(H45F)=Sof(C46B)=Sof(H46D)=Sof(H46E)=Sof(H46F)=1-FVAR(1)
 Sof(C38)=Sof(C39)=Sof(H39)=Sof(C40)=Sof(H40)=Sof(C41)=Sof(C42)=Sof(H42)=
 Sof(C43)=Sof(H43)=Sof(C44)=Sof(H44)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=
 Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=FVAR(1)
 Sof(C55B)=Sof(H55C)=Sof(H55D)=Sof(C56B)=Sof(H56C)=Sof(H56D)=Sof(C57B)=
 Sof(H57C)=Sof(H57D)=Sof(C58B)=Sof(H58C)=Sof(H58D)=Sof(C51B)=Sof(H51C)=
 Sof(H51D)=Sof(C52B)=Sof(H52C)=Sof(H52D)=Sof(C53B)=Sof(H53C)=Sof(H53D)=
 Sof(C54B)=Sof(H54C)=Sof(H54D)=1-FVAR(2)
 Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(C57)=Sof(H57A)=
 Sof(H57B)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(C52)=
 Sof(H52A)=Sof(H52B)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(C54)=Sof(H54A)=Sof(H54B)=
 FVAR(2)
 Sof(C36B)=Sof(H36D)=Sof(H36E)=Sof(H36F)=1-FVAR(3)
 Sof(C36A)=Sof(H36A)=Sof(H36B)=Sof(H36C)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C35(H35), C44(H44), C44B(H44B)
5.b Secondary CH2 refined with riding coordinates:
 C47(H47A,H47B), C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B), C58(H58A,
 H58B), C55B(H55C,H55D), C56B(H56C,H56D), C57B(H57C,H57D), C58B(H58C,H58D),
 C51(H51A,H51B), C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B), C51B(H51C,
 H51D), C52B(H52C,H52D), C53B(H53C,H53D), C54B(H54C,H54D)
5.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), 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), C39B(H39B), C40B(H40B),
 C42B(H42B), C43B(H43B)
5.d Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,
 H50C), C36A(H36A,H36B,H36C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C),
 C36B(H36D,H36E,H36F), C45B(H45D,H45E,H45F), C46B(H46D,H46E,H46F)
;