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_4123286
_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         'C45 H32 Cl Ir O P2, C9 H12, C4 H10 O'
_chemical_formula_sum            'C58 H54 Cl Ir O2 P2'
_chemical_formula_weight         1072.60
_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             2014-02-25
_audit_creation_method
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Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.65611(12)
_cell_length_b                   13.08400(14)
_cell_length_c                   32.0786(3)
_cell_measurement_reflns_used    27866
_cell_measurement_temperature    120
_cell_measurement_theta_max      73.8900
_cell_measurement_theta_min      3.6390
_cell_volume                     4892.26(9)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_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
_diffrn_detector_area_resol_mean 5.3073
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_details
;
  1 omega  -88.00  -34.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3491  125.0000 -180.0000 54

  2 omega  -35.00   31.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3491   38.0000 -150.0000 66

  3 omega -124.00  -10.00   1.0000    1.5300
omega____ theta____ kappa____ phi______ frames
    -      -43.5000  -15.0000 -150.0000 114

  4 omega   50.00   91.00   1.0000    1.5300
omega____ theta____ kappa____ phi______ frames
    -      106.0873  -28.0000 -117.0000 41

  5 omega   94.00  177.00   1.0000    1.5300
omega____ theta____ kappa____ phi______ frames
    -      106.0873  125.0000  -90.0000 83

  6 omega   31.00   89.00   1.0000    1.5300
omega____ theta____ kappa____ phi______ frames
    -      106.0873  -30.0000    0.0000 58

  7 omega   38.00   91.00   1.0000    1.5300
omega____ theta____ kappa____ phi______ frames
    -      106.0873  -30.0000  -60.0000 53

  8 omega   44.00   91.00   1.0000    1.5300
omega____ theta____ kappa____ phi______ frames
    -      106.0873  -30.0000 -150.0000 47

  9 omega   49.00   94.00   1.0000    1.5300
omega____ theta____ kappa____ phi______ frames
    -      106.0873  -95.0000  -90.0000 45

 10 omega   40.00  132.00   1.0000    1.5300
omega____ theta____ kappa____ phi______ frames
    -      106.0873  -77.0000    0.0000 92

 11 omega -111.00  -15.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3491  -57.0000  150.0000 96

 12 omega -115.00  -10.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3491  -77.0000   90.0000 105

 13 omega  -96.00  -71.00   1.0000    1.5300
omega____ theta____ kappa____ phi______ frames
    -      -43.5000  125.0000  -60.0000 25

 14 omega -117.00  -12.00   1.0000    1.5300
omega____ theta____ kappa____ phi______ frames
    -      -43.5000  -77.0000    0.0000 105

 15 omega   61.00  178.00   1.0000    1.5300
omega____ theta____ kappa____ phi______ frames
    -      106.0873   15.0000  150.0000 117

 16 omega   82.00  177.00   1.0000    1.5300
omega____ theta____ kappa____ phi______ frames
    -      106.0873   45.0000   30.0000 95

 17 omega   61.00  178.00   1.0000    1.5300
omega____ theta____ kappa____ phi______ frames
    -      106.0873   15.0000  -90.0000 117

 18 omega   25.00  109.00   1.0000    1.5300
omega____ theta____ kappa____ phi______ frames
    -      106.0873  -95.0000    0.0000 84

 19 omega   35.00  121.00   1.0000    1.5300
omega____ theta____ kappa____ phi______ frames
    -      106.0873 -125.0000  -90.0000 86

 20 omega   78.00  176.00   1.0000    1.5300
omega____ theta____ kappa____ phi______ frames
    -      106.0873   61.0000  -30.0000 98
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1242474000
_diffrn_orient_matrix_UB_12      0.0211497000
_diffrn_orient_matrix_UB_13      0.0138900000
_diffrn_orient_matrix_UB_21      0.0325909000
_diffrn_orient_matrix_UB_22      -0.1112924000
_diffrn_orient_matrix_UB_23      -0.0102605000
_diffrn_orient_matrix_UB_31      0.0311205000
_diffrn_orient_matrix_UB_32      0.0320918000
_diffrn_orient_matrix_UB_33      -0.0448137000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0451
_diffrn_reflns_av_unetI/netI     0.0299
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            46867
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.364
_diffrn_reflns_theta_min         2.755
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.726
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.35620
_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.
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_exptl_crystal_colour            red
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_exptl_crystal_density_diffrn    1.456
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_exptl_crystal_F_000             2168
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.13
_refine_diff_density_max         1.537
_refine_diff_density_min         -1.202
_refine_diff_density_rms         0.104
_refine_ls_abs_structure_details
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 Flack x determined using 4064 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
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_refine_ls_abs_structure_Flack   -0.051(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     577
_refine_ls_number_reflns         9830
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0352
_refine_ls_R_factor_gt           0.0326
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0457P)^2^+7.7791P]
 where P=(Fo^2^+2Fc^2^)/3
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_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0802
_refine_ls_wR_factor_ref         0.0827
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_reflns_Friedel_fraction_max     0.974
_reflns_number_gt                9413
_reflns_number_total             9830
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5106943_si_001.cif
_cod_data_source_block           IrCl(CO)BINAP
_cod_depositor_comments
'Adding full bibliography for 4123286--4123290.cif.'
_cod_database_code               4123286
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'Ir1 Cl1 P2 C45 O1 H32'
_reflns_odcompleteness_completeness 99.98
_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 Secondary CH2 refined with riding coordinates:
 C56(H56a,H56b), C57(H57a,H57b)
2.b Aromatic/amide H refined with riding coordinates:
 C38(H38), C42(H42), C28(H28), C30(H30), C5(H5), C40(H40), C18(H18), C14(H14),
 C23(H23), C32(H32), C31(H31), C7(H7), C16(H16), C8(H8), C44(H44), C47(H47),
 C26(H26), C37(H37), C6(H6), C29(H29), C24(H24), C15(H15), C35(H35), C41(H41),
 C2(H2), C36(H36), C43(H43), C22(H22), C13(H13), C49(H49), C19(H19), C25(H25),
 C34(H34), C3(H3), C51(H51)
2.c Idealised Me refined with riding coordinates:
 C54(H54a,H54b,H54c), C53(H53a,H53b,H53c), C52(H52a,H52b,H52c), C55(H55a,H55b,
 H55c), C58(H58a,H58b,H58c)
;
_shelx_res_checksum              75982
_shelx_hkl_checksum              92561