Addition of a phosphine ligand switches an N-heterocyclic carbene-zirconium catalyst from oligomerization to polymerization of 1-hexene.
Despagnet-Ayoub, Emmanuelle; Henling, Lawrence M.; Labinger, Jay A.; Bercaw, John E.; Dalton transactions (Cambridge, England : 2003) 42 (2013) 15544–15547; doi:10.1039/c3dt52342j

data_7023812
_publ_section_title
;
 Addition of a phosphine ligand switches an N-heterocyclic
 carbene-zirconium catalyst from oligomerization to polymerization of
 1-hexene.
;
_journal_issue                   44
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              15544
_journal_page_last               15547
_journal_paper_doi               10.1039/c3dt52342j
_journal_volume                  42
_journal_year                    2013
_chemical_formula_moiety         'C49 H58 N2 O2 Zr, C4 H10 O'
_chemical_formula_sum            'C53 H68 N2 O3 Zr'
_chemical_formula_weight         872.31
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2013-06-02
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466),
 SHELXL-2013,
 and manual edit
;
_cell_angle_alpha                90
_cell_angle_beta                 111.269(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.4874(19)
_cell_length_b                   21.1068(18)
_cell_length_c                   22.3719(18)
_cell_measurement_reflns_used    9041
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.38
_cell_measurement_theta_min      2.25
_cell_volume                     9455.2(14)
_computing_cell_refinement       'SAINT V8.27B (Bruker-AXS, 2007)'
_computing_data_collection       'APEX2 2013.2-0 (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-2013/2 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXT (Sheldrick, 2012)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 8.33
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.945
_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  0.0941
_diffrn_reflns_av_unetI/netI     0.0802
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            238757
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         32.768
_diffrn_reflns_theta_min         1.646
_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    0.276
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8905
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0689 before and 0.0628 after correction.
The Ratio of minimum to maximum transmission is 0.8905.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.226
_exptl_crystal_description       lump
_exptl_crystal_F_000             3712
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.11
_refine_diff_density_max         1.010
_refine_diff_density_min         -0.727
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.133
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1091
_refine_ls_number_reflns         33053
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.133
_refine_ls_R_factor_all          0.0980
_refine_ls_R_factor_gt           0.0479
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0400P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0924
_refine_ls_wR_factor_ref         0.1049
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21641
_reflns_number_total             33053
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c3dt52342j.txt
_cod_data_source_block           emd45
_cod_depositor_comments
;
The following automatic conversions were performed:

'_diffrn_source_target' value 'MO' changed to 'Mo' according to
/home/saulius/struct/CIF-dictionaries/cif_core.dic dictionary named
'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 1891 2012-01-12 08:04:46Z andrius 
;
_cod_database_code               7023812
_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.a Secondary CH2 refined with riding coordinates:
 C36(H36A,H36B), C43(H43A,H43B), C36B(H36C,H36D), C43B(H43C,H43D), C51(H51A,
 H51B), C52(H52A,H52B), C51B(H51C,H51D), C52B(H52C,H52D)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C11(H11), C13(H13), C25(H25), C27(H27),
 C38(H38), C39(H39), C40(H40), C41(H41), C42(H42), C45(H45), C46(H46), C47(H47),
  C48(H48), C49(H49), C3B(H3B), C4B(H4B), C5B(H5B), C6B(H6B), C11B(H11B),
 C13B(H13B), C25B(H25B), C27B(H27B), C38B(H38B), C39B(H39B), C40B(H40B),
 C41B(H41B), C42B(H42B), C45B(H45B), C46B(H46B), C47B(H47B), C48B(H48B),
 C49B(H49B)
2.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C),
 C35(H35A,H35B,H35C), C15B(H15D,H15E,H15F), C16B(H16D,H16E,H16F), C17B(H17D,
 H17E,H17F), C19B(H19D,H19E,H19F), C20B(H20D,H20E,H20F), C21B(H21D,H21E,H21F),
 C29B(H29D,H29E,H29F), C30B(H30D,H30E,H30F), C31B(H31D,H31E,H31F), C33B(H33D,
 H33E,H33F), C34B(H34D,H34E,H34F), C35B(H35D,H35E,H35F), C50(H50A,H50B,H50C),
 C53(H53A,H53B,H53C), C50B(H50D,H50E,H50F), C53B(H53D,H53E,H53F)
;