Stoichiometric C=O Bond Oxidative Addition of Benzophenone by a Discrete Radical Intermediate To Form a Cobalt(I) Carbene
Seth L. Marquard; Mark W. Bezpalko; Bruce M. Foxman; Christine M. Thomas; Journal of the American Chemical Society 135 (2013) 6018–6021; doi:10.1021/ja4022683

data_4119664
_publ_contact_author_address
;Department of Chemistry
Brandeis University
415 South St. MS 015
Waltham, MA 02454 USA
;
_publ_contact_author_email       thomasc@brandeis.edu
_publ_contact_author_fax         781-736-2516
_publ_contact_author_name        'Christine M. Thomas'
_publ_contact_author_phone       781-736-2576
_publ_section_title
;
 Stoichiometric C=O Bond Oxidative Addition of Benzophenone by a Discrete
 Radical Intermediate To Form a Cobalt(I) Carbene
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6018
_journal_page_last               6021
_journal_paper_doi               10.1021/ja4022683
_journal_volume                  135
_journal_year                    2013
_chemical_formula_moiety         'C60.50 H91 Co1 N3 O1 P3 Zr1'
_chemical_formula_sum            'C60.5 H91 Co N3 O P3 Zr'
_chemical_formula_weight         1119.48
_space_group_IT_number           15
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     other
_audit_creation_date             2012-11-26
_audit_creation_method           CRYSTALS_ver_14.52
_cell_angle_alpha                90
_cell_angle_beta                 97.893(5)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   43.887(4)
_cell_length_b                   13.0471(12)
_cell_length_c                   20.6865(16)
_cell_measurement_reflns_used    3115
_cell_measurement_temperature    135
_cell_measurement_theta_max      24
_cell_measurement_theta_min      3
_cell_volume                     11732.8(18)
_computing_cell_refinement       'Apex2 (Bruker AXS, 2006)'
_computing_data_collection       'Apex2 (Bruker AXS, 2006)'
_computing_data_reduction        'Apex2 (Bruker AXS, 2006)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'Superflip (Palatinus & Chapuis, 2007)'
_diffrn_ambient_temperature      135
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Bruker Kappa Apex2'
_diffrn_measurement_method       '\f & \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.133
_diffrn_reflns_limit_h_max       57
_diffrn_reflns_limit_h_min       -57
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            58425
_diffrn_reflns_theta_full        27.500
_diffrn_reflns_theta_max         28.061
_diffrn_reflns_theta_min         1.988
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.583
_exptl_absorpt_correction_T_max  0.94
_exptl_absorpt_correction_T_min  0.94
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
; 
 Analytical Absorption (De Meulenaer & Tompa, 1965) 
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.267
_exptl_crystal_description       prism
_exptl_crystal_F_000             4760
_exptl_crystal_size_max          0.170
_exptl_crystal_size_mid          0.110
_exptl_crystal_size_min          0.100
_refine_diff_density_max         1.46
_refine_diff_density_min         -2.00
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.0000
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     628
_refine_ls_number_reflns         14159
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.1202
_refine_ls_R_factor_gt           0.0563
_refine_ls_shift/su_max          0.0018558
_refine_ls_shift/su_mean         0.0000674
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.04P)^2^ +11.70P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1176
_refine_ls_wR_factor_gt          0.0995
_refine_ls_wR_factor_ref         0.1176
_reflns_limit_h_max              57
_reflns_limit_h_min              -57
_reflns_limit_k_max              17
_reflns_limit_k_min              0
_reflns_limit_l_max              27
_reflns_limit_l_min              0
_reflns_number_gt                8350
_reflns_number_total             14159
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   0.00
_oxford_diffrn_Wilson_scale      0.00
_oxford_refine_ls_r_factor_ref   0.1202
_oxford_refine_ls_scale          0.035027(2)
_oxford_reflns_number_all        14159
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title 'slmIII_120b_0m in C2/c'
_cod_data_source_file            ja4022683_si_002_2.cif
_cod_data_source_block           4
_cod_original_cell_volume        11732.8(17)
_cod_original_sg_symbol_Hall     '-C 2yc '
_cod_original_sg_symbol_H-M      'C 1 2/c 1 '
_cod_original_formula_sum        'C60.50 H91 Co1 N3 O1 P3 Zr1'
_cod_database_code               4119664
_iucr_refine_instructions_details_constraints
;
BLOCK 
CONT SCALE 
CONT ZR   (    1 ,X'S,U'S)  UNTIL C    (   58 ) 
CONT C    (  60 ,X'S,U[ISO])  UNTIL C    (   62 ) 
CONT H(391,X'S,U[ISO]) UNTIL H(393) 
RIDE C   (   3,X'S) H   (  31,X'S) H   (  32,X'S) H   (  33,X'S) 
RIDE C   (   4,X'S) H   (  41,X'S) 
RIDE C   (   6,X'S) H   (  61,X'S) H   (  62,X'S) H   (  63,X'S) 
RIDE C   (   7,X'S) H   (  71,X'S) 
RIDE C   (   9,X'S) H   (  91,X'S) H   (  92,X'S) H   (  93,X'S) 
RIDE C   (  10,X'S) H   ( 101,X'S) 
RIDE C   (  11,X'S) H   ( 111,X'S) H   ( 112,X'S) H   ( 113,X'S) 
RIDE C   (  12,X'S) H   ( 121,X'S) H   ( 122,X'S) H   ( 123,X'S) 
RIDE C   (  13,X'S) H   ( 131,X'S) 
RIDE C   (  14,X'S) H   ( 141,X'S) H   ( 142,X'S) H   ( 143,X'S) 
RIDE C   (  15,X'S) H   ( 151,X'S) H   ( 152,X'S) H   ( 153,X'S) 
RIDE C   (  18,X'S) H   ( 181,X'S) H   ( 182,X'S) H   ( 183,X'S) 
RIDE C   (  19,X'S) H   ( 191,X'S) 
RIDE C   (  21,X'S) H   ( 211,X'S) H   ( 212,X'S) H   ( 213,X'S) 
RIDE C   (  22,X'S) H   ( 221,X'S) 
RIDE C   (  24,X'S) H   ( 241,X'S) H   ( 242,X'S) H   ( 243,X'S) 
RIDE C   (  25,X'S) H   ( 251,X'S) 
RIDE C   (  26,X'S) H   ( 261,X'S) H   ( 262,X'S) H   ( 263,X'S) 
RIDE C   (  27,X'S) H   ( 271,X'S) H   ( 272,X'S) H   ( 273,X'S) 
RIDE C   (  28,X'S) H   ( 281,X'S) 
RIDE C   (  29,X'S) H   ( 291,X'S) H   ( 292,X'S) H   ( 293,X'S) 
RIDE C   (  30,X'S) H   ( 301,X'S) H   ( 302,X'S) H   ( 303,X'S) 
RIDE C   (  33,X'S) H   ( 331,X'S) H   ( 332,X'S) H   ( 333,X'S) 
RIDE C   (  34,X'S) H   ( 341,X'S) 
RIDE C   (  36,X'S) H   ( 361,X'S) H   ( 362,X'S) H   ( 363,X'S) 
RIDE C   (  37,X'S) H   ( 371,X'S) 
REM RIDE C   (  39,X'S) H   ( 391,X'S) H   ( 392,X'S) H   ( 393,X'S) 
RIDE C   (  42,X'S) H   ( 421,X'S) 
RIDE C   (  43,X'S) H   ( 431,X'S) 
RIDE C   (  44,X'S) H   ( 441,X'S) 
RIDE C   (  45,X'S) H   ( 451,X'S) 
RIDE C   (  46,X'S) H   ( 461,X'S) 
RIDE C   (  48,X'S) H   ( 481,X'S) 
RIDE C   (  49,X'S) H   ( 491,X'S) 
RIDE C   (  50,X'S) H   ( 501,X'S) 
RIDE C   (  51,X'S) H   ( 511,X'S) 
RIDE C   (  52,X'S) H   ( 521,X'S) 
RIDE C   (  53,X'S) H   ( 531,X'S) 
RIDE C   (  54,X'S) H   ( 541,X'S) H   ( 542,X'S) H   ( 543,X'S) 
RIDE C   (  55,X'S) H   ( 551,X'S) H   ( 552,X'S) H   ( 553,X'S) 
RIDE C   (  56,X'S) H   ( 561,X'S) 
RIDE C   (  57,X'S) H   ( 571,X'S) H   ( 572,X'S) H   ( 573,X'S) 
RIDE C   (  58,X'S) H   ( 581,X'S) H   ( 582,X'S) H   ( 583,X'S) 
END                                                                             
;
_iucr_refine_instructions_details_restraints
;
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
ANGLE 109.000000 , 0.300000 = C(60) TO C(61) TO C(62) 
DISTANCE 1.540000 , 0.015000 = C(60) TO C(60,2,1,1) 
END                                                                             
;