Bis(diisopropylphosphinomethyl)amine Nickel(II) and Nickel(0) Complexes: Coordination Chemistry, Reactivity, and Catalytic Decarbonylative C‒H Arylation of Benzoxazole
Kruckenberg, Achim; Wadepohl, Hubert; Gade, Lutz H.; Organometallics 32 (2013) 5153–; doi:10.1021/om400711d

data_4081436
_publ_section_title
;
 Bis(diisopropylphosphinomethyl)amine Nickel(II) and Nickel(0) Complexes:
 Coordination Chemistry, Reactivity, and Catalytic Decarbonylative C--H
 Arylation of Benzoxazole
;
_journal_issue                   18
_journal_name_full               Organometallics
_journal_page_first              5153
_journal_paper_doi               10.1021/om400711d
_journal_volume                  32
_journal_year                    2013
_chemical_formula_moiety         'C20 H46 N Ni O P2, C32 H12 B F24'
_chemical_formula_sum            'C52 H58 B F24 N Ni O P2'
_chemical_formula_weight         1300.45
_chemical_properties_physical    air-sensitive
_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_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_ak31
_audit_creation_date
;
'Thu May 31 12:47:41 2012'
;
_audit_update_record             'Thu Jul  4 11:17:50 CEST 2013'
_cell_angle_alpha                90
_cell_angle_beta                 91.681(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.9568(3)
_cell_length_b                   12.8435(2)
_cell_length_c                   34.2531(8)
_cell_measurement_reflns_used    10842
_cell_measurement_temperature    110(1)
_cell_measurement_theta_max      71.8023
_cell_measurement_theta_min      3.4097
_cell_volume                     5697.6(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
;
_computing_molecular_graphics
;
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.
;
_computing_publication_material
'encif (Wadepohl, 2009-13); encifer 1.4 (CCDC, 2011)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_temperature      110(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            'Agilent EOS'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details
;
  1 omega  -64.00  -38.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000   60.0000 26

  2 omega  -17.00   19.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000   60.0000 36

  3 omega   -8.00   32.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000 -120.0000 40

  4 omega  -24.00    1.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -30.0000  -80.0000  -57.0000 25

  5 omega   11.00   45.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       42.0000   79.0000  -60.0000 34

  6 omega  -39.00   18.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   25.0000  -60.0000 57

  7 omega  -50.00   29.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   38.0000  120.0000 79

  8 omega  -47.00   26.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   77.0000  -60.0000 73

  9 omega  -76.00   30.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   19.0000 -120.0000 106

 10 omega   52.00   77.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       55.1171  -80.0000  -65.0000 25

 11 omega  -16.00   76.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       55.1171  -80.0000   29.0000 92

 12 omega    2.00   35.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000  -79.0000 -108.0000 33

 13 omega   25.00   96.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000  -79.0000  106.0000 71

 14 omega   54.00   80.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000  -79.0000 -108.0000 26

 15 omega   18.00   43.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       82.0000  -79.0000  -35.0000 25

 16 omega   70.00   96.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       82.0000  -79.0000  -35.0000 26

 17 omega   56.00   82.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       94.0000  -79.0000   14.0000 26

 18 omega   59.00   85.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      102.0000  -80.0000  153.0000 26

 19 omega   87.00  113.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -80.0000  166.0000 26

 20 omega   78.00  105.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -80.0000 -126.0000 27

 21 omega   48.00  114.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -80.0000 -166.0000 66

 22 omega   74.00  106.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -80.0000  -17.0000 32

 23 omega   39.00   86.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -38.0000   60.0000 47

 24 omega   40.00   69.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -80.0000  -17.0000 29

 25 omega   88.00  171.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   50.0000   30.0000 83

 26 omega   47.00   92.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -25.0000  -90.0000 45

 27 omega   60.00   86.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -80.0000  -32.0000 26

 28 omega   91.00  117.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   50.0000  -30.0000 26

 29 omega  152.00  178.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   50.0000  -30.0000 26

 30 omega   40.00   91.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -25.0000 -150.0000 51

 31 omega   42.00  142.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -80.0000  -72.0000 100

 32 omega   65.00  142.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -80.0000   71.0000 77

 33 omega   48.00   74.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -25.0000  -30.0000 26

 34 omega   40.00   80.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -25.0000  150.0000 40

 35 omega   59.00  106.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -80.0000   32.0000 47

 36 omega   52.00   86.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -38.0000 -180.0000 34

 37 omega   44.00   93.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -38.0000    0.0000 49

 38 omega   55.00   84.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -38.0000   90.0000 29

 39 omega   39.00  176.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -12.0000    0.0000 137

 40 omega   80.00  105.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -80.0000  126.0000 25

 41 omega  -19.00   80.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       10.0000   76.0000  118.0000 99

 42 omega  -15.00   84.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       14.0000   76.0000   45.0000 99

 43 omega   19.00   49.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   78.0000 -130.0000 30

 44 omega   19.00   49.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   78.0000  -15.0000 30

 45 omega   19.00   49.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   78.0000   32.0000 30

 46 omega   19.00   47.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   79.0000  121.0000 28

 47 omega   18.00   43.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   80.0000  -33.0000 25

 48 omega   24.00  124.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000 -163.0000 100

 49 omega   23.00   49.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   78.0000   62.0000 26

 50 omega   28.00  128.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   77.0000  -26.0000 100

 51 omega   29.00  128.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   75.0000   85.0000 99

 52 omega   29.00  128.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   76.0000 -120.0000 99

 53 omega   28.00  128.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   77.0000  143.0000 100

 54 omega    7.00  109.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       78.0000  -79.0000 -178.0000 102

;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_UB_11      0.0234323000
_diffrn_orient_matrix_UB_12      0.0127404000
_diffrn_orient_matrix_UB_13      -0.0435797000
_diffrn_orient_matrix_UB_21      -0.0840329000
_diffrn_orient_matrix_UB_22      0.0845134000
_diffrn_orient_matrix_UB_23      -0.0038702000
_diffrn_orient_matrix_UB_31      0.0808332000
_diffrn_orient_matrix_UB_32      0.0841968000
_diffrn_orient_matrix_UB_33      0.0104929000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0855
_diffrn_reflns_av_unetI/netI     0.0637
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            66315
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.948
_diffrn_reflns_theta_min         3.413
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.085
_exptl_absorpt_correction_T_max  0.977
_exptl_absorpt_correction_T_min  0.881
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.516
_exptl_crystal_description       plate
_exptl_crystal_F_000             2656
_exptl_crystal_size_max          0.1596
_exptl_crystal_size_mid          0.0866
_exptl_crystal_size_min          0.0222
_refine_diff_density_max         1.024
_refine_diff_density_min         -0.639
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     788
_refine_ls_number_reflns         11047
_refine_ls_number_restraints     39
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0931
_refine_ls_R_factor_gt           0.0643
_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^)+(0.0409P)^2^+11.0173P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1279
_refine_ls_wR_factor_ref         0.1418
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8161
_reflns_number_total             11047
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om400711d_si_002.cif
_cod_data_source_block           ga_ak31
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               4081436
_audit_block_refno               1508
_audit_block_usercomment         'AK_BG005, plate, yellow'
_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(F4A) \\sim Ueq, Uanis(F5A) \\sim Ueq, Uanis(F6A) \\sim Ueq, Uanis(F4B) \\sim Ueq, Uanis(F5B) \\sim Ueq, Uanis(F6B) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.01
3. Same fragment restrains
{F4A, F5A, F6A}
as
{F4B, F5B, F6B}
4. Others
 Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(1)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C3(H3), C6(H6), C9(H9), C12(H12)
5.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B),
 C20(H20A,H20B)
5.c Aromatic/amide H refined with riding coordinates:
 C22(H22), C24(H24), C26(H26), C32(H32), C34(H34), C36(H36), C42(H42),
 C44(H44), C46(H46), C52(H52), C54(H54), C56(H56)
5.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C10(H10A,
 H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C15(H15A,H15B,H15C)
;
_shelx_estimated_absorpt_t_max   0.819
_shelx_estimated_absorpt_t_min   0.819
_shelx_res_checksum              2972
_shelxl_version_number           2013-3
_cell_oxdiff_length_a            12.9586(4)
_cell_oxdiff_length_b            12.8407(4)
_cell_oxdiff_length_c            34.2547(10)
_cell_oxdiff_angle_alpha         90.012(2)
_cell_oxdiff_angle_beta          91.630(2)
_cell_oxdiff_angle_gamma         90.010(2)
_cell_oxdiff_volume              5697.6(3)
_cell_oxdiff_measurement_reflns_used 10842
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_theta     66.97
_reflns_odcompleteness_iscentric 1