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_4123288
_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         'C56 H52 Cl2 Ir2 O4 P4, 2(C H2 Cl2)'
_chemical_formula_sum            'C58 H56 Cl6 Ir2 O4 P4'
_chemical_formula_weight         1538.00
_chemical_name_systematic
;
 ?
;
_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_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2014-02-26
_audit_creation_method
;
Olex2 1.2
(compiled 2014.02.17 svn.r2891 for OlexSys, GUI svn.r4777)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.335(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.0362(3)
_cell_length_b                   25.6332(4)
_cell_length_c                   17.1736(3)
_cell_measurement_reflns_used    13715
_cell_measurement_temperature    120
_cell_measurement_theta_max      51.3310
_cell_measurement_theta_min      3.0910
_cell_volume                     5738.62(19)
_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)
;
_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)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_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 0.557
_diffrn_measured_fraction_theta_max 0.927
_diffrn_measurement_details
;
  1 omega  -88.00  -57.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       -0.1562  178.0000 -150.0000 31

  2 omega  -16.00   74.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       -0.1562   77.0000   60.0000 90

  3 omega  104.00  136.00   1.0000    3.3100
omega____ theta____ kappa____ phi______ frames
    -       62.6093  125.0000  -90.0000 32

  4 omega   98.00  135.00   1.0000    3.3100
omega____ theta____ kappa____ phi______ frames
    -       62.6093  125.0000   30.0000 37

  5 omega   75.00  140.00   1.0000    3.3100
omega____ theta____ kappa____ phi______ frames
    -       62.6093   38.0000   90.0000 65

  6 omega  -89.00   -5.00   1.0000    3.3100
omega____ theta____ kappa____ phi______ frames
    -      -62.9218  125.0000 -180.0000 84

  7 omega -139.00  -34.00   1.0000    3.3100
omega____ theta____ kappa____ phi______ frames
    -      -62.9218  -57.0000 -120.0000 105

  8 omega  -91.00  -35.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       -0.1562 -178.0000  120.0000 56

  9 omega  -31.00   76.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       -0.1562   57.0000    0.0000 107

 10 omega   94.00  139.00   1.0000    3.3100
omega____ theta____ kappa____ phi______ frames
    -       62.6093  125.0000 -150.0000 45

 11 omega -140.00  -34.00   1.0000    3.3100
omega____ theta____ kappa____ phi______ frames
    -      -62.9218  -38.0000  -30.0000 106

 12 omega -139.00  -73.00   1.0000    3.3100
omega____ theta____ kappa____ phi______ frames
    -      -62.9218  -57.0000  150.0000 66

 13 omega  -50.00   15.00   1.0000    3.3100
omega____ theta____ kappa____ phi______ frames
    -      -62.9218   38.0000   30.0000 65
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0068592000
_diffrn_orient_matrix_UB_12      0.0280386000
_diffrn_orient_matrix_UB_13      -0.0791288000
_diffrn_orient_matrix_UB_21      0.0330135000
_diffrn_orient_matrix_UB_22      -0.0514768000
_diffrn_orient_matrix_UB_23      -0.0387740000
_diffrn_orient_matrix_UB_31      -0.1132838000
_diffrn_orient_matrix_UB_32      -0.0133183000
_diffrn_orient_matrix_UB_33      -0.0166437000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0768
_diffrn_reflns_av_unetI/netI     0.0524
_diffrn_reflns_Laue_measured_fraction_full 0.557
_diffrn_reflns_Laue_measured_fraction_max 0.927
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            23750
_diffrn_reflns_point_group_measured_fraction_full 0.557
_diffrn_reflns_point_group_measured_fraction_max 0.927
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         51.368
_diffrn_reflns_theta_min         3.097
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.841
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.24219
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
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_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.780
_exptl_crystal_description       needle
_exptl_crystal_F_000             3008
_exptl_crystal_size_max          0.179
_exptl_crystal_size_mid          0.057
_exptl_crystal_size_min          0.038
_refine_diff_density_max         1.691
_refine_diff_density_min         -1.398
_refine_diff_density_rms         0.145
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     667
_refine_ls_number_reflns         5789
_refine_ls_number_restraints     1704
_refine_ls_restrained_S_all      0.940
_refine_ls_R_factor_all          0.0495
_refine_ls_R_factor_gt           0.0435
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0622P)^2^+33.9641P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1096
_refine_ls_wR_factor_ref         0.1152
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5122
_reflns_number_total             5789
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5106943_si_001.cif
_cod_data_source_block           '[ircl(co)dppp]2o2'
_cod_depositor_comments
'Adding full bibliography for 4123286--4123290.cif.'
_cod_original_cell_volume        5738.6(2)
_cod_database_code               4123288
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 93.49
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     50.38
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C61-C56 \\sim C61-C60 \\sim C60-C59 \\sim C59-C58 \\sim C58-C57 \\sim C57-C56
\\sim C45-C44 \\sim C49-C44
 \\sim C49-C48 \\sim C46-C45 \\sim C47-C46 \\sim C48-C47 \\sim C16-C15 \\sim
C15-C14 \\sim C19-C14 \\sim C19-
 C18 \\sim C18-C17 \\sim C17-C16 \\sim C28-C27 \\sim C29-C28 \\sim C30-C29
\\sim C31-C30 \\sim C31-C26 ~
 C27-C26 \\sim C25-C24 \\sim C25-C20 \\sim C24-C23 \\sim C23-C22 \\sim C22-C21
\\sim C21-C20 \\sim C4-C3 ~
 C5-C4 \\sim C6-C5 \\sim C7-C6 \\sim C8-C7 \\sim C8-C3 \\sim C35-C34 \\sim
C36-C35 \\sim C37-C36 \\sim C38-C37
 \\sim C38-C33 \\sim C34-C33 \\sim C51-C50 \\sim C52-C51 \\sim C53-C52 \\sim
C54-C53 \\sim C55-C54 \\sim C55-C50
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C51 \\sim C50 \\sim C53 \\sim C52 \\sim C54 \\sim C55 \\sim C34 \\sim C35 \\sim
C36 \\sim C37 \\sim C38 \\sim C33 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8
\\sim C3 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C31
\\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C14 \\sim C19 \\sim C18
\\sim C17 \\sim C16 \\sim C15 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48
\\sim C49 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C56 \\sim C57: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C14) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C17)
\\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C26) \\sim Ueq,
Uanis(C27) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30)
\\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C49) \\sim Ueq,
Uanis(C48) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C45)
\\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C58) \\sim Ueq,
Uanis(C59) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C20)
\\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C23) \\sim Ueq,
Uanis(C22) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4)
\\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq,
Uanis(C8) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C52)
\\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C55) \\sim Ueq,
Uanis(C33) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C36)
\\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C38) \\sim Ueq: with sigma of 0.1 and
sigma for terminal atoms of 0.2
Uanis(C52) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C55)
\\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C51) \\sim Ueq: with sigma of 0.1 and
sigma for terminal atoms of 0.2
4.a Secondary CH2 refined with riding coordinates:
 C12(H12a,H12b), C11(H11a,H11b), C42(H42a,H42b), C40(H40a,H40b), C10(H10a,
 H10b), C41(H41a,H41b), C64(H64a,H64b), C1(H1a,H1b)
4.b Aromatic/amide H refined with riding coordinates:
 C61(H61), C48(H48), C46(H46), C45(H45), C49(H49), C24(H24), C15(H15),
 C23(H23), C19(H19), C7(H7), C21(H21), C38(H38), C59(H59), C30(H30), C25(H25),
 C47(H47), C22(H22), C8(H8), C57(H57), C31(H31), C4(H4), C60(H60), C37(H37),
 C6(H6), C16(H16), C58(H58), C27(H27), C29(H29), C28(H28), C18(H18), C34(H34),
 C35(H35), C5(H5), C36(H36), C17(H17), C55(H55), C54(H54), C51(H51), C53(H53),
 C52(H52)
;
_shelx_res_checksum              4259
_shelx_hkl_checksum              80743
_olex2_computing_structure_refinement_long 'ShelXL (Sheldrick, 2008)'