Bimetallic Coordination Insertion Polymerization of Unprotected Polar Monomers: Copolymerization of Amino Olefins and Ethylene by Dinickel Bisphenoxyiminato Catalysts
Madalyn R. Radlauer; Aya K. Buckley; Lawrence M. Henling; Theodor Agapie; Journal of the American Chemical Society 135 (2013) 3784–3787; doi:10.1021/ja4004816

data_4119469
_publ_contact_author_address
;
Beckman Institute
Caltech 139-74
Pasadena CA 91125
USA
;
_publ_contact_author_email       xray@caltech.edu
_publ_contact_author_name        'Xray Staff'
_publ_section_title
;
 Bimetallic Coordination Insertion Polymerization of Unprotected Polar
 Monomers: Copolymerization of Amino Olefins and Ethylene by Dinickel
 Bisphenoxyiminato Catalysts
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3784
_journal_page_last               3787
_journal_paper_doi               10.1021/ja4004816
_journal_volume                  135
_journal_year                    2013
_chemical_formula_moiety         'C63 H92 N2 Ni2 O2 P2, 3.4(C7 H8)'
_chemical_formula_sum            'C86.8 H119.2 N2 Ni2 O2 P2'
_chemical_formula_weight         1395.93
_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     dual
_audit_creation_date             2012-12-03
_audit_creation_method
;
  Olex2 1.2
  (compiled Nov  5 2012 18:25:38, GUI svn.r4372),
 SHELXL-2012,
 and manual edit
;
_cell_angle_alpha                91.115(7)
_cell_angle_beta                 97.107(8)
_cell_angle_gamma                101.877(7)
_cell_formula_units_Z            4
_cell_length_a                   13.284(4)
_cell_length_b                   21.951(7)
_cell_length_c                   27.971(9)
_cell_measurement_reflns_used    5019
_cell_measurement_temperature    100
_cell_measurement_theta_max      23.92
_cell_measurement_theta_min      2.28
_cell_volume                     7912(4)
_computing_cell_refinement       'SAINT V8.27B (Bruker-AXS, 2007)'
_computing_data_collection       'APEX2 2012.10-0 (Bruker-AXS, 2007)'
_computing_data_reduction        'SAINT V8.27B (Bruker-AXS, 2007)'
_computing_molecular_graphics    'DIAMOND 3 (Crystal Impact, 1999)'
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
 and SHELXTL (Bruker-AXS, 2007)
;
_computing_structure_refinement
;
SHELXL-2012/7 (Sheldrick, 2012)
PLATON (Spek, 2005)
;
_computing_structure_solution    'SHELXT (Sheldrick, 2012)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 8.33
_diffrn_measured_fraction_theta_full 0.704
_diffrn_measured_fraction_theta_max 0.607
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0812
_diffrn_reflns_av_unetI/netI     0.2108
_diffrn_reflns_Laue_measured_fraction_full 0.704
_diffrn_reflns_Laue_measured_fraction_max 0.607
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            31564
_diffrn_reflns_point_group_measured_fraction_full 0.704
_diffrn_reflns_point_group_measured_fraction_max 0.607
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.679
_diffrn_reflns_theta_min         1.752
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.563
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.6104
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0811 before and 0.0590 after correction.
The Ratio of minimum to maximum transmission is 0.6104.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_density_diffrn    1.171
_exptl_crystal_description       block
_exptl_crystal_F_000             3024
_exptl_crystal_size_max          0.74
_exptl_crystal_size_mid          0.47
_exptl_crystal_size_min          0.30
_platon_squeeze_details
;
Added 6 toluenes to unit cell contents, although small
voids are obviously not.
;
_refine_diff_density_max         1.878
_refine_diff_density_min         -1.306
_refine_diff_density_rms         0.177
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.915
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     815
_refine_ls_number_reflns         22465
_refine_ls_number_restraints     96
_refine_ls_restrained_S_all      1.944
_refine_ls_R_factor_all          0.2353
_refine_ls_R_factor_gt           0.1615
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0600P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3432
_refine_ls_wR_factor_ref         0.3640
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10461
_reflns_number_total             22465
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja4004816_si_003.cif
_cod_data_source_block           mrr30
_cod_depositor_comments
;
The following automatic conversions were performed:

'_diffrn_source_target' value 'MO' changed to 'Mo' according to the
built-in table from CIF Core dictionary named 'cif_core.dic' version
2.4.1 from 2010-06-29.

Automatic conversion script
Id: cif_fix_values 2281 2013-09-26 08:29:07Z andrius 
;
_cod_original_formula_sum        'C86.80 H119.20 N2 Ni2 O2 P2'
_cod_database_code               4119469
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H16 of C16, H17 of C17, H18 of C18, H19 of C19, H20 of C20, H23 of C23, H24
  of C24, H25 of C25, H26 of C26, H27 of C27, H30A of C30A, H27A of C27A, H25A
  of C25A, H24A of C24A, H23A of C23A, H20A of C20A, H15A of C15A, H13A of C13A,
   H4A of C4A, H36A of C36A, H38A of C38A, H43A of C43A, H46A of C46A, H47A of
  C47A, H48A of C48A, H50A of C50A, H53A of C53A, H43B of C43B, H46B of C46B,
  H47B of C47B, H48B of C48B, H50B of C50B, H53B of C53B, H2 of C2, H3 of C3,
  H4 of C4, H5 of C5, H6 of C6, H9 of C9, H10 of C10, H11 of C11, H12 of C12,
  H13 of C13, H4B of C4B, H13B of C13B, H15B of C15B, H20B of C20B, H38B of
  C38B, H36B of C36B, H30B of C30B, H27B of C27B, H25B of C25B, H24B of C24B,
  H23B of C23B
 At 1.5 times of:
  {H21A,H21B,H21C} of C21, {H28G,H28H,H28I} of C28, {H32D,H32E,H32F} of C32A,
  {H31D,H31E,H31F} of C31A, {H29D,H29E,H29F} of C29A, {H28D,H28E,H28F} of C28A,
  {H19D,H19E,H19F} of C19A, {H18D,H18E,H18F} of C18A, {H17D,H17E,H17F} of C17A,
  {H9AA,H9AB,H9AC} of C9A, {H8AA,H8AB,H8AC} of C8A, {H7AA,H7AB,H7AC} of C7A,
  {H40D,H40E,H40F} of C40A, {H41D,H41E,H41F} of C41A, {H42D,H42E,H42F} of C42A,
  {H51D,H51E,H51F} of C51A, {H52D,H52E,H52F} of C52A, {H54D,H54E,H54F} of C54A,
  {H55D,H55E,H55F} of C55A, {H56D,H56E,H56F} of C56A, {H57D,H57E,H57F} of C57A,
  {H58D,H58E,H58F} of C58A, {H41A,H41B,H41C} of C41B, {H42A,H42B,H42C} of C42B,
  {H51A,H51B,H51C} of C51B, {H52A,H52B,H52C} of C52B, {H54A,H54B,H54C} of C54B,
  {H55A,H55B,H55C} of C55B, {H56A,H56B,H56C} of C56B, {H57A,H57B,H57C} of C57B,
  {H58A,H58B,H58C} of C58B, {H59A,H59B,H59C} of C59B, {H60A,H60B,H60C} of C60B,
  {H61A,H61B,H61C} of C61B, {H62A,H62B,H62C} of C62B, {H63A,H63B,H63C} of C63B,
  {H7A,H7B,H7C} of C7, {H14A,H14B,H14C} of C14, {H59D,H59E,H59F} of C59A, {H60D,
  H60E,H60F} of C60A, {H61D,H61E,H61F} of C61A, {H62D,H62E,H62F} of C62A, {H63D,
  H63E,H63F} of C63A, {H7BA,H7BB,H7BC} of C7B, {H8BA,H8BB,H8BC} of C8B, {H9BA,
  H9BB,H9BC} of C9B, {H17A,H17B,H17C} of C17B, {H18A,H18B,H18C} of C18B, {H19A,
  H19B,H19C} of C19B, {H40A,H40B,H40C} of C40B, {H32A,H32B,H32C} of C32B, {H31A,
  H31B,H31C} of C31B, {H29A,H29B,H29C} of C29B, {H28A,H28B,H28C} of C28B
2. Uiso/Uaniso restraints and constraints
Uanis(Ni1A) ~ Ueq, Uanis(Ni2A) ~ Ueq, Uanis(Ni1B) ~ Ueq, Uanis(Ni2B) ~ Ueq, 
Uanis(N1A) ~ Ueq, Uanis(N2A) ~ Ueq, Uanis(N1B) ~ Ueq, Uanis(N2B) ~ Ueq, 
Uanis(O1A) ~ Ueq, Uanis(O2A) ~ Ueq, Uanis(O1B) ~ Ueq, Uanis(O2B) ~ Ueq, 
Uanis(P1A) ~ Ueq, Uanis(P2A) ~ Ueq, Uanis(P1B) ~ Ueq, Uanis(P2B) ~ Ueq: 
with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(Ni1B) ~ Ueq, Uanis(O1B) ~ Ueq, Uanis(N1B) ~ Ueq, Uanis(P1B) ~ Ueq, 
Uanis(P2B) ~ Ueq, Uanis(Ni2B) ~ Ueq, Uanis(N2B) ~ Ueq, Uanis(O2B) ~ Ueq, 
Uanis(P1A) ~ Ueq, Uanis(Ni1A) ~ Ueq, Uanis(N1A) ~ Ueq, Uanis(O1A) ~ Ueq, 
Uanis(O2A) ~ Ueq, Uanis(N2A) ~ Ueq, Uanis(Ni2A) ~ Ueq, Uanis(P2A) ~ Ueq: 
with sigma of 0.001 and sigma for terminal atoms of 0.002
3. others
 Sof(C22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24)=Sof(C25)=Sof(H25)=Sof(C26)=
 Sof(H26)=Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28G)=Sof(H28H)=Sof(H28I)
4.a Ternary CH refined with riding coordinates:
 C27A(H27A), C30A(H30A), C50A(H50A), C53A(H53A), C27B(H27B), C30B(H30B),
 C50B(H50B), C53B(H53B)
4.b Aromatic/amide H refined with riding coordinates:
 C4A(H4A), C13A(H13A), C15A(H15A), C20A(H20A), C23A(H23A), C24A(H24A),
 C25A(H25A), C36A(H36A), C38A(H38A), C43A(H43A), C46A(H46A), C47A(H47A),
 C48A(H48A), C4B(H4B), C13B(H13B), C15B(H15B), C20B(H20B), C23B(H23B),
 C24B(H24B), C25B(H25B), C36B(H36B), C38B(H38B), C43B(H43B), C46B(H46B),
 C47B(H47B), C48B(H48B), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C9(H9),
 C10(H10), C11(H11), C12(H12), C13(H13), C16(H16), C17(H17), C18(H18), C19(H19),
  C20(H20), C23(H23), C24(H24), C25(H25), C26(H26), C27(H27)
4.c Idealised Me refined with riding coordinates:
 C41B(H41A,H41B,H41C)
4.d Idealised Me refined as rotating group:
 C7A(H7AA,H7AB,H7AC), C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,H9AC), C17A(H17D,H17E,
 H17F), C18A(H18D,H18E,H18F), C19A(H19D,H19E,H19F), C28A(H28D,H28E,H28F),
 C29A(H29D,H29E,H29F), C31A(H31D,H31E,H31F), C32A(H32D,H32E,H32F), C40A(H40D,
 H40E,H40F), C41A(H41D,H41E,H41F), C42A(H42D,H42E,H42F), C51A(H51D,H51E,H51F),
 C52A(H52D,H52E,H52F), C54A(H54D,H54E,H54F), C55A(H55D,H55E,H55F), C56A(H56D,
 H56E,H56F), C57A(H57D,H57E,H57F), C58A(H58D,H58E,H58F), C59A(H59D,H59E,H59F),
 C60A(H60D,H60E,H60F), C61A(H61D,H61E,H61F), C62A(H62D,H62E,H62F), C63A(H63D,
 H63E,H63F), C7B(H7BA,H7BB,H7BC), C8B(H8BA,H8BB,H8BC), C9B(H9BA,H9BB,H9BC),
 C17B(H17A,H17B,H17C), C18B(H18A,H18B,H18C), C19B(H19A,H19B,H19C), C28B(H28A,
 H28B,H28C), C29B(H29A,H29B,H29C), C31B(H31A,H31B,H31C), C32B(H32A,H32B,H32C),
 C40B(H40A,H40B,H40C), C42B(H42A,H42B,H42C), C51B(H51A,H51B,H51C), C52B(H52A,
 H52B,H52C), C54B(H54A,H54B,H54C), C55B(H55A,H55B,H55C), C56B(H56A,H56B,H56C),
 C57B(H57A,H57B,H57C), C58B(H58A,H58B,H58C), C59B(H59A,H59B,H59C), C60B(H60A,
 H60B,H60C), C61B(H61A,H61B,H61C), C62B(H62A,H62B,H62C), C63B(H63A,H63B,H63C),
 C7(H7A,H7B,H7C), C14(H14A,H14B,H14C), C21(H21A,H21B,H21C), C28(H28G,H28H,H28I)
;
_shelx_estimated_absorpt_t_max   0.849
_shelx_estimated_absorpt_t_min   0.681
_shelx_res_checksum              16053
_shelxl_version_number           2012-6