Experimental and theoretical mechanistic investigation of the iridium-catalyzed dehydrogenative decarbonylation of primary alcohols.
Olsen, Esben P. K.; Singh, Thishana; Harris, Pernille; Andersson, Pher G.; Madsen, Robert; Journal of the American Chemical Society 137 (2015) 834–842; doi:10.1021/ja5106943

data_4123287
_publ_section_title
;
 Experimental and theoretical mechanistic investigation of the
 iridium-catalyzed dehydrogenative decarbonylation of primary alcohols.
;
_journal_issue                   2
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              834
_journal_page_last               842
_journal_paper_doi               10.1021/ja5106943
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety         'C26 H27 Cl Ir P'
_chemical_formula_sum            'C26 H27 Cl Ir P'
_chemical_formula_weight         598.09
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-04-23
_audit_creation_method
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Olex2 1.2
(compiled 2014.03.12 svn.r2899 for OlexSys, GUI svn.r4796)
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_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.09492(15)
_cell_length_b                   16.2329(4)
_cell_length_c                   16.8117(3)
_cell_measurement_reflns_used    5212
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      28.6760
_cell_measurement_theta_min      3.0640
_cell_volume                     2209.13(8)
_computing_cell_refinement
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
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_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
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_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
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_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
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_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      120(2)
_diffrn_detector_area_resol_mean 5.3073
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.887
_diffrn_measurement_details
;
  1 omega  -15.00   92.00   1.0000    2.3100
omega____ theta____ kappa____ phi______ frames
    -       14.1467   38.0000 -120.0000 107

  2 omega   -1.00   25.00   1.0000    2.3100
omega____ theta____ kappa____ phi______ frames
    -       14.1467   77.0000    0.0000 26

  3 omega   77.00  105.00   1.0000    2.3100
omega____ theta____ kappa____ phi______ frames
    -       14.1467 -178.0000 -150.0000 28
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0058072000
_diffrn_orient_matrix_UB_12      -0.0186808000
_diffrn_orient_matrix_UB_13      0.0380313000
_diffrn_orient_matrix_UB_21      0.0175939000
_diffrn_orient_matrix_UB_22      -0.0384206000
_diffrn_orient_matrix_UB_23      -0.0182288000
_diffrn_orient_matrix_UB_31      0.0856493000
_diffrn_orient_matrix_UB_32      0.0091558000
_diffrn_orient_matrix_UB_33      0.0011785000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
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_diffrn_reflns_av_unetI/netI     0.0568
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.887
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            8277
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.826
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.179
_diffrn_reflns_theta_min         2.729
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    6.247
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75577
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.798
_exptl_crystal_description       block
_exptl_crystal_F_000             1168
_exptl_crystal_size_max          0.406
_exptl_crystal_size_mid          0.169
_exptl_crystal_size_min          0.161
_refine_diff_density_max         0.788
_refine_diff_density_min         -0.779
_refine_diff_density_rms         0.143
_refine_ls_abs_structure_details
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 Flack x determined using 1795 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
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_refine_ls_abs_structure_Flack   -0.018(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     262
_refine_ls_number_reflns         4916
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.0313
_refine_ls_R_factor_gt           0.0288
_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^)+(0.0105P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
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_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0513
_refine_ls_wR_factor_ref         0.0527
_reflns_Friedel_coverage         0.649
_reflns_Friedel_fraction_full    0.961
_reflns_Friedel_fraction_max     0.747
_reflns_number_gt                4690
_reflns_number_total             4916
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5106943_si_001.cif
_cod_data_source_block           IrCl(cyclooctadiene)PPh3
_cod_depositor_comments
'Adding full bibliography for 4123286--4123290.cif.'
_cod_database_code               4123287
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C20 H17 Cl1 Ir1 O2 P1'
_reflns_odcompleteness_completeness 99.73
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C22(H22), C23(H23), C26(H26), C27(H27)
2.b Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B), C29(H29A,H29B), C24(H24A,H24B), C25(H25A,H25B)
2.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C11(H11), C4(H4), C19(H19), C18(H18), C17(H17), C8(H8), C15(H15),
 C21(H21), C7(H7), C14(H14), C12(H12), C6(H6), C13(H13), C5(H5)
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