Catalytic Hydrosilylation of Ketones Using a Co/Zr Heterobimetallic Complex: Evidence for an Unusual Mechanism Involving Ketyl Radicals
Zhou, Wen; Marquard, Seth L.; Bezpalko, Mark W.; Foxman, Bruce M.; Thomas, Christine M.; Organometallics 32 (2013) 1766–; doi:10.1021/om301194g

data_4080400
_publ_section_title
;
 Catalytic Hydrosilylation of Ketones Using a Co/Zr Heterobimetallic
 Complex: Evidence for an Unusual Mechanism Involving Ketyl Radicals
;
_journal_issue                   6
_journal_name_full               Organometallics
_journal_page_first              1766
_journal_paper_doi               10.1021/om301194g
_journal_volume                  32
_journal_year                    2013
_chemical_formula_moiety         'C116 H170 Co2 N10 O2 P6 Zr2'
_chemical_formula_sum            'C116 H170 Co2 N10 O2 P6 Zr2'
_chemical_formula_weight         2222.75
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     other
_audit_creation_date             2012-11-12
_audit_creation_method           CRYSTALS_ver_14.43
_cell_angle_alpha                89.884(2)
_cell_angle_beta                 83.360(2)
_cell_angle_gamma                82.805(2)
_cell_formula_units_Z            1
_cell_length_a                   12.8526(5)
_cell_length_b                   15.6573(5)
_cell_length_c                   18.0649(7)
_cell_measurement_reflns_used    9939
_cell_measurement_temperature    135
_cell_measurement_theta_max      30
_cell_measurement_theta_min      3
_cell_volume                     3582.2(2)
_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 0.997
_diffrn_measured_fraction_theta_max 0.991
_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  0.043
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            20831
_diffrn_reflns_theta_full        29.465
_diffrn_reflns_theta_max         30.067
_diffrn_reflns_theta_min         1.135
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.478
_exptl_absorpt_correction_T_max  0.92
_exptl_absorpt_correction_T_min  0.87
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
; 
 Analytical Absorption (De Meulenaer & Tompa, 1965) 
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.030
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1176
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.290
_exptl_crystal_size_min          0.170
_platon_squeeze_details
;
During the structure solution, electron density difference maps 
revealed that there were considerable disordered solvent 
molecules which could not be successfully modeled.  From history, 
the remaining solvate was likely diethyl ether in a volume of 
1002.1 \%A3 per unit cell (28.0%).  It appeared that the cavity 
area contained ca. 4-5 ether molecules, located near the center 
of symmetry at (0, 0, 0).  Modeling with or without restraints was 
unsuccessful, as was step by step acquisition of peaks using successive 
electron density difference maps.  Thus, the structure factors were 
modified using the PLATON SQUEEZE technique, in order to produce a 
?solvate-free? structure factor set.  PLATON reported a total e
lectron density of 201 e- per unit cell, likely representing 4-5 ether 
molecules, consistent with our earlier observations.  Use of the 
SQUEEZE technique resulted in a decrease of ca. 2.2 % in R.   
;
_refine_diff_density_max         0.99
_refine_diff_density_min         -0.73
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   0.9823
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     648
_refine_ls_number_reflns         20831
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0652
_refine_ls_R_factor_gt           0.0433
_refine_ls_shift/su_max          0.0085374
_refine_ls_shift/su_mean         0.0001453
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.06P)^2^ + 3.49P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1273
_refine_ls_wR_factor_gt          0.1170
_refine_ls_wR_factor_ref         0.1273
_reflns_limit_h_max              18
_reflns_limit_h_min              -17
_reflns_limit_k_max              22
_reflns_limit_k_min              -22
_reflns_limit_l_max              25
_reflns_limit_l_min              0
_reflns_number_gt                15293
_reflns_number_total             20831
_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   0.0652
_oxford_refine_ls_scale          0.11333(2)
_oxford_reflns_number_all        20831
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title 'SLMIII_100_0m in P-1'
_cod_data_source_file            om301194g_si_002.cif
_cod_data_source_block           slmIII_100
_cod_depositor_comments
;
The following automatic conversions were performed:

'_atom_sites_solution_primary' value 'Other' changed to 'other'
according to /home/saulius/struct/CIF-dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 1891 2012-01-12 08:04:46Z andrius 
;
_cod_original_sg_symbol_Hall     '-P 1 '
_cod_original_sg_symbol_H-M      'P -1 '
_cod_database_code               4080400
_iucr_refine_instructions_details_constraints
;
BLOCK 
CONT SCALE 
CONT ZR   (    1 ,X'S,U'S)  UNTIL C    (   45 ) 
CONT C    (   46 ,X'S,U[ISO])  UNTIL C    (   47 ) 
CONT C    (   48 ,X'S,U'S)  UNTIL C    (   62 ) 
CONT C    (   63 ,X'S,U[ISO])  UNTIL C    (   64 ) 
SUMFIX PART(1001,OCC) AND PART(1002,OCC) 
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   (   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) 
RIDE C   (  39,X'S) H   ( 391,X'S) H   ( 392,X'S) H   ( 393,X'S) 
RIDE C   (  40,X'S) H   ( 401,X'S) 
RIDE C   (  41,X'S) H   ( 411,X'S) H   ( 412,X'S) H   ( 413,X'S) 
RIDE C   (  42,X'S) H   ( 421,X'S) H   ( 422,X'S) H   ( 423,X'S) 
RIDE C   (  43,X'S) H   ( 431,X'S) 
RIDE C   (  44,X'S) H   ( 441,X'S) H   ( 442,X'S) H   ( 443,X'S) 
RIDE C   (  45,X'S) H   ( 451,X'S) H   ( 452,X'S) H   ( 453,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) 
RIDE C   (  55,X'S) H   ( 551,X'S) 
RIDE C   (  56,X'S) H   ( 561,X'S) 
RIDE C   (  58,X'S) H   ( 581,X'S) 
RIDE C   (  59,X'S) H   ( 591,X'S) 
RIDE C   (  60,X'S) H   ( 601,X'S) 
RIDE C   (  61,X'S) H   ( 611,X'S) 
RIDE C   (  62,X'S) H   ( 621,X'S) 
RIDE C   (  63,X'S) H   ( 631,X'S) H   ( 632,X'S) H   ( 633,X'S) 
RIDE C   (  64,X'S) H   ( 641,X'S) H   ( 642,X'S) H   ( 643,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) 
END                                                                             
;