β-Diketiminate Rare Earth Borohydride Complexes: Synthesis, Structure, and Catalytic Activity in the Ring-Opening Polymerization of ε-Caprolactone and Trimethylene Carbonate
Schmid, Matthias; Guillaume, Sophie M.; Roesky, Peter W.; Organometallics 33 (2014) 5392–; doi:10.1021/om500708x

data_4084716
_publ_contact_author
;
      Prof. Dr. Peter W. Roesky
      Karlsruher Institut fuer Technologie (KIT), CS
      Institut fuer Anorganische Chemie (AOC)
      Lehrstuhl fuer Anorganische Funktionsmaterialien
      Engesserstr. 15, Geb. 30.45
      76131 Karlsruhe 
      Bundesrepublik Deutschland
;
_publ_section_title
;
 \b-Diketiminate Rare Earth Borohydride Complexes: Synthesis, Structure,
 and Catalytic Activity in the Ring-Opening Polymerization of
 \e-Caprolactone and Trimethylene Carbonate
;
_journal_issue                   19
_journal_name_full               Organometallics
_journal_page_first              5392
_journal_paper_doi               10.1021/om500708x
_journal_volume                  33
_journal_year                    2014
_chemical_formula_moiety         'C37 H61 B N2 O2 Sm'
_chemical_formula_sum            'C37 H61 B N2 O2 Sm'
_chemical_formula_weight         727.03
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-08-26
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                76.521(3)
_cell_angle_beta                 84.648(3)
_cell_angle_gamma                85.551(3)
_cell_formula_units_Z            2
_cell_length_a                   8.7602(3)
_cell_length_b                   12.3497(4)
_cell_length_c                   17.8330(6)
_cell_measurement_reflns_used    26855
_cell_measurement_temperature    150
_cell_measurement_theta_max      27.25
_cell_measurement_theta_min      2.28
_cell_volume                     1864.85(11)
_computing_cell_refinement       'STOE X-AREA, PLATON (A.L.Spek, 2005)'
_computing_data_collection       'STOE X-AREA'
_computing_data_reduction        'STOE X-RED & LANA, PLATON (A.L.Spek, 2005)'
_computing_molecular_graphics    'Diamond 2/3, Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'MS Word, Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2008)'
_computing_structure_solution
;
SHELXS (Sheldrick, 2008)
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      150
_diffrn_detector                 'image plate (34cm diameter)'
_diffrn_detector_area_resol_mean 6.67
_diffrn_detector_type            STOE
_diffrn_measured_fraction_theta_full 0.821
_diffrn_measured_fraction_theta_max 0.823
_diffrn_measurement_device       '2-circle goniometer'
_diffrn_measurement_device_type  'STOE IPDS 2'
_diffrn_measurement_method       'area detector'
_diffrn_radiation_collimation    '0.5mm monocapillary'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0429
_diffrn_reflns_av_unetI/netI     0.0354
_diffrn_reflns_Laue_measured_fraction_full 0.821
_diffrn_reflns_Laue_measured_fraction_max 0.823
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            19975
_diffrn_reflns_point_group_measured_fraction_full 0.821
_diffrn_reflns_point_group_measured_fraction_max 0.823
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.999
_diffrn_reflns_theta_min         2.339
_diffrn_source                   'sealed tube, 12x0.4mm long-fine focus'
_exptl_absorpt_coefficient_mu    1.606
_exptl_absorpt_correction_T_max  0.8650
_exptl_absorpt_correction_T_min  0.7239
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details   'STOE X-Red & X-Shape'
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.295
_exptl_crystal_description       plate
_exptl_crystal_F_000             760
_exptl_crystal_size_max          0.395
_exptl_crystal_size_mid          0.178
_exptl_crystal_size_min          0.062
_refine_diff_density_max         0.423
_refine_diff_density_min         -0.828
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.992
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     623
_refine_ls_number_reflns         6032
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      0.993
_refine_ls_R_factor_all          0.0341
_refine_ls_R_factor_gt           0.0268
_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^)+(0.0437P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0636
_refine_ls_wR_factor_ref         0.0656
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5259
_reflns_number_total             6032
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om500708x_si_002.cif
_cod_data_source_block           ms262
_cod_database_code               4084716
_shelxl_version_number           2014-3
_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. Uiso/Uaniso restraints and constraints
Uanis(C32A) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C35B) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
3. Others
 Fixed Sof: C6A(0.5) C11A(0.5) C10A(0.5) H10A(0.5) C9A(0.5) H9A(0.5) C8A(0.5)
 H8A(0.5) C7A(0.5) C6B(0.5) C11B(0.5) C10B(0.5) H10B(0.5) C9B(0.5) H9B(0.5)
 C8B(0.5) H8B(0.5) C7B(0.5) C12A(0.5) H12A(0.5) C12B(0.5) H12B(0.5) C13A(0.5)
 H13A(0.5) H13B(0.5) H13C(0.5) C13B(0.5) H13D(0.5) H13E(0.5) H13F(0.5)
 C14A(0.5) H14A(0.5) H14B(0.5) H14C(0.5) C14B(0.5) H14D(0.5) H14E(0.5)
 H14F(0.5) C15A(0.5) H15A(0.5) C15B(0.5) H15B(0.5) C16A(0.5) H16A(0.5)
 H16B(0.5) H16C(0.5) C16B(0.5) H16D(0.5) H16E(0.5) H16F(0.5) C17A(0.5)
 H17A(0.5) H17B(0.5) H17C(0.5) C17B(0.5) H17D(0.5) H17E(0.5) H17F(0.5) H24(0.5)
 H24A(0.5) C25A(0.5) H25A(0.5) H25B(0.5) H25C(0.5) C25B(0.5) H25D(0.5)
 H25E(0.5) H25F(0.5) C26A(0.5) H26A(0.5) H26B(0.5) H26C(0.5) C26B(0.5)
 H26D(0.5) H26E(0.5) H26F(0.5) C27A(0.5) H27A(0.5) C27B(0.5) H27B(0.5)
 C28A(0.5) H28A(0.5) H28B(0.5) H28C(0.5) C28B(0.5) H28D(0.5) H28E(0.5)
 H28F(0.5) C29A(0.5) H29A(0.5) H29B(0.5) H29C(0.5) C29B(0.5) H29D(0.5)
 H29E(0.5) H29F(0.5) C30A(0.5) H30A(0.5) H30B(0.5) C30B(0.5) H30C(0.5)
 H30D(0.5) C31A(0.5) H31A(0.5) H31B(0.5) C31B(0.5) H31C(0.5) H31D(0.5)
 C32A(0.5) H32A(0.5) H32B(0.5) C32B(0.5) H32C(0.5) H32D(0.5) C33A(0.5)
 H33A(0.5) H33B(0.5) C33B(0.5) H33C(0.5) H33D(0.5) C34A(0.5) H34A(0.5)
 H34B(0.5) C34B(0.5) H34C(0.5) H34D(0.5) C35A(0.5) H35A(0.5) H35B(0.5)
 C35B(0.5) H35C(0.5) H35D(0.5) C36A(0.5) H36A(0.5) H36B(0.5) C36B(0.5)
 H36C(0.5) H36D(0.5) C37A(0.5) H37A(0.5) H37B(0.5) C37B(0.5) H37C(0.5) H37D(0.5)
4.a Ternary CH refined with riding coordinates:
 C12A(H12A), C12B(H12B), C15A(H15A), C15B(H15B), C24(H24), C24(H24A),
 C27A(H27A), C27B(H27B)
4.b Secondary CH2 refined with riding coordinates:
 C30A(H30A,H30B), C30B(H30C,H30D), C31A(H31A,H31B), C31B(H31C,H31D), C32A(H32A,
 H32B), C32B(H32C,H32D), C33A(H33A,H33B), C33B(H33C,H33D), C34A(H34A,H34B),
 C34B(H34C,H34D), C35A(H35A,H35B), C35B(H35C,H35D), C36A(H36A,H36B), C36B(H36C,
 H36D), C37A(H37A,H37B), C37B(H37C,H37D)
4.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C10A(H10A), C9A(H9A), C8A(H8A), C10B(H10B), C9B(H9B), C8B(H8B),
 C20(H20), C21(H21), C22(H22)
4.d Fitted hexagon refined as free rotating group:
 C6A(C11A,C10A,C9A,C8A,C7A), C6B(C11B,C10B,C9B,C8B,C7B)
4.e Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C5(H5A,H5B,H5C), C13A(H13A,H13B,H13C), C13B(H13D,H13E,H13F),
 C14A(H14A,H14B,H14C), C14B(H14D,H14E,H14F), C16A(H16A,H16B,H16C), C16B(H16D,
 H16E,H16F), C17A(H17A,H17B,H17C), C17B(H17D,H17E,H17F), C25A(H25A,H25B,H25C),
 C25B(H25D,H25E,H25F), C26A(H26A,H26B,H26C), C26B(H26D,H26E,H26F), C28A(H28A,
 H28B,H28C), C28B(H28D,H28E,H28F), C29A(H29A,H29B,H29C), C29B(H29D,H29E,H29F)
;
_shelx_res_checksum              97102
_shelx_hkl_checksum              60281
_olex2_submission_special_instructions 'No special instructions were received'