Molecular and Silica-Supported Molybdenum Alkyne Metathesis Catalysts: Influence of Electronics and Dynamics on Activity Revealed by Kinetics, Solid-State NMR, and Chemical Shift Analysis.
Estes, Deven P.; Gordon, Christopher P.; Fedorov, Alexey; Liao, Wei-Chih; Ehrhorn, Henrike; Bittner, Celine; Zier, Manuel Luca; Bockfeld, Dirk; Chan, Ka Wing; Eisenstein, Odile; Raynaud, Christophe; Tamm, Matthias; Copéret, Christophe; Journal of the American Chemical Society 139 (2017) 17597–17607; doi:10.1021/jacs.7b09934

data_4131746
_publ_section_title
;
 Molecular and Silica-Supported Molybdenum Alkyne Metathesis Catalysts:
 Influence of Electronics and Dynamics on Activity Revealed by Kinetics,
 Solid-State NMR, and Chemical Shift Analysis.
;
_journal_issue                   48
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              17597
_journal_page_last               17607
_journal_paper_doi               10.1021/jacs.7b09934
_journal_volume                  139
_journal_year                    2017
_chemical_formula_sum            'C18 H9 F27 Mo O3'
_chemical_formula_weight         882.19
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.2097(6)
_cell_length_b                   16.6236(8)
_cell_length_c                   11.1509(6)
_cell_measurement_reflns_used    25333
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      75.7670
_cell_measurement_theta_min      4.7570
_cell_volume                     2634.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_publication_material
;
 WinGX v2014.1 (L. J. Farrugia, J. Appl. Cryst., 2012, 45, 849-854.)
;
_computing_structure_refinement
;
 SHELXL-2014/7 (G. M. Sheldrick, Acta Cryst. (2008), A64, 112-122)'
;
_computing_structure_solution
;
 SHELXT-2014/7 (G. M. Sheldrick, Acta Cryst., 2008, A64, 112-122)
;
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 10.3543
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Oxford Diffraction Xcalibur, Atlas, Nova'
_diffrn_measurement_method       '\w scan'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0502
_diffrn_reflns_av_unetI/netI     0.0142
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            51545
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.161
_diffrn_reflns_theta_min         4.775
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Nova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.163
_exptl_absorpt_correction_T_max  0.977
_exptl_absorpt_correction_T_min  0.968
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    2.225
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1704
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.180
_exptl_crystal_size_min          0.160
_refine_diff_density_max         0.371
_refine_diff_density_min         -0.955
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     306
_refine_ls_number_reflns         2847
_refine_ls_number_restraints     108
_refine_ls_restrained_S_all      1.225
_refine_ls_R_factor_all          0.0328
_refine_ls_R_factor_gt           0.0298
_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^)+(0.0549P)^2^+1.1928P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0792
_refine_ls_wR_factor_ref         0.0827
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2573
_reflns_number_total             2847
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b09934_si_001.cif
_cod_data_source_block           he15fr
_cod_database_code               4131746
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.372
_shelx_estimated_absorpt_t_max   0.439
_oxdiff_exptl_absorpt_empirical_full_min 0.580
_oxdiff_exptl_absorpt_empirical_full_max 1.638
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_shelx_res_checksum              10827
_shelx_hkl_checksum              27593