Mechanism of Molybdenum-Mediated Carbon Monoxide Deoxygenation and Coupling: Mono- and Dicarbyne Complexes Precede C-O Bond Cleavage and C-C Bond Formation.
Buss, Joshua A.; Agapie, Theodor; Journal of the American Chemical Society 138 (2016) 16466–16477; doi:10.1021/jacs.6b10535

data_4131174
_publ_section_title
;
 Mechanism of Molybdenum-Mediated Carbon Monoxide Deoxygenation and
 Coupling: Mono- and Dicarbyne Complexes Precede C-O Bond Cleavage and C-C
 Bond Formation.
;
_journal_issue                   50
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16466
_journal_page_last               16477
_journal_paper_doi               10.1021/jacs.6b10535
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety         'C38 H58 Mo O2 P2 Si2, C4 H10'
_chemical_formula_sum            'C42 H68 Mo O2 P2 Si2'
_chemical_formula_weight         819.02
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-06-09
_audit_creation_method
;
Olex2 1.2
(compiled 2014.05.21 svn.r2940 for OlexSys, GUI svn.r4846),
SHELXL-2014,
and manual edit
;
_cell_angle_alpha                76.202(2)
_cell_angle_beta                 75.565(2)
_cell_angle_gamma                72.413(2)
_cell_formula_units_Z            2
_cell_length_a                   12.8387(8)
_cell_length_b                   13.2552(8)
_cell_length_c                   14.3715(8)
_cell_measurement_reflns_used    9981
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      33.95
_cell_measurement_theta_min      2.40
_cell_volume                     2222.3(2)
_computing_cell_refinement       'SAINT v8.34A (Bruker-AXS, 2007)'
_computing_data_collection       'APEX2 v2014.11-0 (Bruker-AXS, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker-AXS, 2007)'
_computing_molecular_graphics    'DIAMOND 3 (Crystal Impact, 1999)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'XT-2014/4 (Sheldrick, 2012)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'CMOS Area Detector'
_diffrn_detector_area_resol_mean 10.24
_diffrn_detector_type            'Bruker PHOTON 100 CMOS'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'multilayer mirrors'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0793
_diffrn_reflns_av_unetI/netI     0.0766
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            110566
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         35.631
_diffrn_reflns_theta_min         2.399
_diffrn_source                   'I\mS HB micro-focus sealed tube'
_diffrn_source_current           1
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatech I\mS HB'
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.453
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9606
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS-2014/5 (Sheldrick, 2014)'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.224
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             872
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.725
_refine_diff_density_min         -0.741
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     475
_refine_ls_number_reflns         20489
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0825
_refine_ls_R_factor_gt           0.0447
_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^)+(0.0253P)^2^+0.8971P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0721
_refine_ls_wR_factor_ref         0.0802
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14895
_reflns_number_total             20489
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b10535_si_001.cif
_cod_data_source_block           10
_cod_database_code               4131174
_shelxl_version_number           2014-7
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.939
_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, All C(H,H,H,H,H,H) groups
2. Others
 Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(H42D)=Sof(H42E)=Sof(H42F)=Sof(C40B)=
 Sof(H40C)=Sof(H40D)=Sof(C41B)=Sof(H41C)=Sof(H41D)=1-FVAR(1)
 Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C40A)=
 Sof(H40A)=Sof(H40B)=Sof(C41A)=Sof(H41A)=Sof(H41B)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C19(H19), C22(H22), C25(H25), C28(H28)
3.b Secondary CH2 refined with riding coordinates:
 C40A(H40A,H40B), C41A(H41A,H41B), C40B(H40C,H40D), C41B(H41C,H41D)
3.c Me refined with riding coordinates:
 C39(H39A,H39B,H39C), C39(H39D,H39E,H39F), C42(H42A,H42B,H42C), C42(H42D,H42E,
 H42F)
3.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C14(H14), C15(H15), C16(H16), C17(H17)
3.e Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C),
 C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_original_sample_id JAB_4-278
_olex2_submission_special_instructions 'No special instructions were received'