Nickel-Catalyzed Decarbonylation of Acylsilanes.
Nakatani, Syun; Ito, Yuri; Sakurai, Shun; Kodama, Takuya; Tobisu, Mamoru; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c00772

data_4038361
_publ_section_title
;
 Nickel-Catalyzed Decarbonylation of Acylsilanes.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c00772
_journal_year                    2020
_chemical_formula_moiety         'C40 H64 Ni O P2 Si'
_chemical_formula_sum            'C40 H64 Ni O P2 Si'
_chemical_formula_weight         709.65
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-03-06
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.02.24 svn.r3390 for Rigaku Oxford Diffraction, GUI svn.r5318)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.1046(9)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   26.7679(3)
_cell_length_b                   10.09187(12)
_cell_length_c                   28.8990(3)
_cell_measurement_reflns_used    18436
_cell_measurement_temperature    123
_cell_measurement_theta_max      75.8620
_cell_measurement_theta_min      4.6540
_cell_volume                     7801.46(15)
_computing_cell_refinement       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      123
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.962
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -24.00  17.00   0.50   12.96    --   47.45 -63.00  55.00   82
  2  \w     23.00  64.00   0.50   12.96    --   47.45 -63.00  55.00   82
  3  \w      2.00  57.00   0.50   51.83    --   70.50 -63.00  55.00  110
  4  \w    -25.00  28.00   0.50   12.96    --   47.45 -37.00 -30.00  106
  5  \w     51.00  76.00   0.50   12.96    --   47.45  63.00-167.00   50
  6  \w     74.00  99.00   0.50   51.83    --   70.50  63.00-167.00   50
  7  \w     87.00 119.00   0.50   12.96    --   47.45 125.00  30.00   64
  8  \w     74.00 113.00   0.50   12.96    --   47.45 125.00 120.00   78
  9  \w    -48.00  20.00   0.50   12.96    --  -47.45  63.00-167.00  136
 10  \w    -99.00 -74.00   0.50   12.96    --  -47.45 -63.00  55.00   50
 11  \w   -101.00 -48.00   0.50   51.83    -- -106.00  37.00  30.00  106
 12  \w    -84.00 -33.00   0.50   51.83    -- -106.00  57.00  90.00  102
 13  \w    -68.00 -42.00   0.50   51.83    -- -106.00 125.00   0.00   52
 14  \w    -64.00 -39.00   0.50   51.83    -- -106.00 125.00 -60.00   50
 15  \w   -120.00 -91.00   0.50   51.83    -- -106.00  57.00  90.00   58
 16  \w   -164.00-100.00   0.50   51.83    -- -106.00 -57.00 150.00  128
 17  \w   -170.00-117.00   0.50   51.83    -- -106.00 -63.00  55.00  106
 18  \w   -176.00 -91.00   0.50   51.83    -- -106.00 -57.00  30.00  170
 19  \w   -176.00-104.00   0.50   51.83    -- -106.00 -19.00  90.00  144
 20  \w   -123.00 -33.00   0.50   51.83    -- -106.00  63.00-167.00  180
 21  \w   -170.00-134.00   0.50   51.83    -- -106.00 -57.00-180.00   72
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0287938000
_diffrn_orient_matrix_UB_12      -0.0620411000
_diffrn_orient_matrix_UB_13      -0.0417496000
_diffrn_orient_matrix_UB_21      0.0273453000
_diffrn_orient_matrix_UB_22      0.0930189000
_diffrn_orient_matrix_UB_23      -0.0329232000
_diffrn_orient_matrix_UB_31      0.0416807000
_diffrn_orient_matrix_UB_32      -0.1039566000
_diffrn_orient_matrix_UB_33      -0.0045101000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0383
_diffrn_reflns_av_unetI/netI     0.0308
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            27653
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.527
_diffrn_reflns_theta_min         4.423
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.993
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54897
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.43a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.208
_exptl_crystal_description       plate
_exptl_crystal_F_000             3072
_exptl_crystal_size_max          0.111
_exptl_crystal_size_mid          0.071
_exptl_crystal_size_min          0.029
_refine_diff_density_max         0.372
_refine_diff_density_min         -0.381
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     409
_refine_ls_number_reflns         7887
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0371
_refine_ls_R_factor_gt           0.0329
_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^)+(0.0544P)^2^+3.9979P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0893
_refine_ls_wR_factor_ref         0.0920
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7018
_reflns_number_total             7887
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00772_si_002.cif
_cod_data_source_block           x200335_yir01-050-1-2
_cod_original_cell_volume        7801.45(15)
_cod_database_code               4038361
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C40 H64 O1 P2 Si1 Ni1'
_chemical_oxdiff_usercomment     'X200335_YIR01-050-1 C40 H64 O1 P2 Si1 Ni1'
_diffrn_oxdiff_ac3_digest_frames
;
0117bb87e0865ba38b8e7f516506bab69e000254424
;
_diffrn_oxdiff_ac3_digest_hkl
;
01ad543b16d1a549bcaeb834cb27f75df083f1
;
_reflns_odcompleteness_completeness 99.72
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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 Ternary CH refined with riding coordinates:
 C18(H18), C28(H28), C34(H34), C40(H40)
2.b Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C25(H25A,H25B), C21(H21A,H21B), C41(H41A,H41B), C31(H31A,
 H31B), C45(H45A,H45B), C35(H35A,H35B), C37(H37A,H37B), C32(H32A,H32B),
 C19(H19A,H19B), C29(H29A,H29B), C33(H33A,H33B), C44(H44A,H44B), C30(H30A,H30B),
  C42(H42A,H42B), C22(H22A,H22B), C23(H23A,H23B), C43(H43A,H43B), C38(H38A,
 H38B), C20(H20A,H20B), C36(H36A,H36B), C39(H39A,H39B)
2.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C5(H5), C7(H7), C6(H6), C10(H10), C8(H8), C3(H3)
2.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C15(H15A,H15B,H15C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.737
_oxdiff_exptl_absorpt_empirical_full_min 0.530