Characterization and Reactivity Studies of Dinuclear Iridium Hydride Complexes Prepared from Iridium Catalysts with N,P and C,N Ligands under Hydrogenation Conditions
Gruber, Stefan; Neuburger, Markus; Pfaltz, Andreas; Organometallics 32 (2013) 4702–; doi:10.1021/om4007467

data_4081468
_publ_section_title
;
 Characterization and Reactivity Studies of Dinuclear Iridium Hydride
 Complexes Prepared from Iridium Catalysts with N,P and C,N Ligands under
 Hydrogenation Conditions
;
_journal_issue                   16
_journal_name_full               Organometallics
_journal_page_first              4702
_journal_paper_doi               10.1021/om4007467
_journal_volume                  32
_journal_year                    2013
_chemical_absolute_configuration ad
_chemical_formula_moiety
'2(C32 H12 B F24), C46 H61 Cl Ir2 N4 O4 P2, 2(C H2 Cl2)'
_chemical_formula_sum            'C112 H89 B2 Cl5 F48 Ir2 N4 O4 P2'
_chemical_formula_weight         3109.12
_space_group_IT_number           1
_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     direct
_cell_angle_alpha                92.544(3)
_cell_angle_beta                 113.818(2)
_cell_angle_gamma                92.667(3)
_cell_formula_units_Z            1
_cell_length_a                   14.2328(7)
_cell_length_b                   14.5307(7)
_cell_length_c                   15.9379(8)
_cell_measurement_reflns_used    9932
_cell_measurement_temperature    123
_cell_measurement_theta_max      31
_cell_measurement_theta_min      3
_cell_volume                     3005.0(3)
_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    'SIR92 (Altomare et al., 1994)'
_diffrn_ambient_temperature      123
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Bruker Kappa Apex2'
_diffrn_measurement_method       \w/2\q
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.034
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            172350
_diffrn_reflns_theta_full        30.075
_diffrn_reflns_theta_max         34.970
_diffrn_reflns_theta_min         1.915
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.477
_exptl_absorpt_correction_T_max  0.64
_exptl_absorpt_correction_T_min  0.46
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Siemens, 1996)'
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.718
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1529
_exptl_crystal_size_max          0.368
_exptl_crystal_size_mid          0.311
_exptl_crystal_size_min          0.180
_refine_diff_density_max         2.47
_refine_diff_density_min         -2.93
_refine_ls_abs_structure_details 'Flack (1983), 25024 Friedel-pairs'
_refine_ls_abs_structure_Flack   -0.0073(15)
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   0.9621
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1687
_refine_ls_number_reflns         41743
_refine_ls_number_restraints     211
_refine_ls_R_factor_all          0.0350
_refine_ls_R_factor_gt           0.0267
_refine_ls_shift/su_max          0.0010973
_refine_ls_shift/su_mean         0.0000541
_refine_ls_structure_factor_coef F
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F) + ( 0.01P)^2^ + 0.00P] 
 ,where P=(max(Fo,0) + 2Fc)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0497
_refine_ls_wR_factor_gt          0.0261
_refine_ls_wR_factor_ref         0.0255
_reflns_limit_h_max              22
_reflns_limit_h_min              -22
_reflns_limit_k_max              23
_reflns_limit_k_min              -23
_reflns_limit_l_max              25
_reflns_limit_l_min              -25
_reflns_number_gt                43294
_reflns_number_total             51163
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   1.03
_oxford_diffrn_Wilson_scale      241.55
_oxford_refine_ls_r_factor_ref   0.0255
_oxford_refine_ls_scale          0.069487(17)
_oxford_reflns_number_all        51080
_oxford_reflns_threshold_expression_ref I>3.0\s(I)
_cod_data_source_file            om4007467_si_002.cif
_cod_data_source_block           1
_cod_database_code               4081468
_iucr_refine_instruction_details_constraints
;
BLOCK SCALE X'S, U'S 
CONT ENANTIO 
EQUIVALENCE PART(1001, OCC) 
CONTINUE    PART(1002, OCC) 
WEIGHT -1   PART(1002, OCC) 
EQUIVALENCE PART(2001, OCC) 
CONTINUE    PART(2002, OCC) 
WEIGHT -1   PART(2002, OCC) 
RIDE C   (   1,X'S) H   (  11,X'S) 
RIDE C   (   2,X'S) H   (  21,X'S) 
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) H   (  42,X'S) H   (  43,X'S) 
RIDE C   (   5,X'S) H   (  51,X'S) H   (  52,X'S) 
RIDE C   (   8,X'S) H   (  81,X'S) H   (  82,X'S) H   (  83,X'S) 
RIDE C   (   9,X'S) H   (  91,X'S) H   (  92,X'S) H   (  93,X'S) 
RIDE C   (  11,X'S) H   ( 111,X'S) 
RIDE C   (  12,X'S) H   ( 121,X'S) 
RIDE C   (  13,X'S) H   ( 131,X'S) 
RIDE C   (  14,X'S) H   ( 141,X'S) 
RIDE C   (  15,X'S) H   ( 151,X'S) 
RIDE C   (  17,X'S) H   ( 171,X'S) 
RIDE C   (  18,X'S) H   ( 181,X'S) 
RIDE C   (  19,X'S) H   ( 191,X'S) 
RIDE C   (  20,X'S) H   ( 201,X'S) 
RIDE C   (  21,X'S) H   ( 211,X'S) 
RIDE C   (  22,X'S) H   ( 221,X'S) 
RIDE C   (  23,X'S) H   ( 231,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) H   ( 252,X'S) H   ( 253,X'S) 
RIDE C   (  26,X'S) H   ( 261,X'S) H   ( 262,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   (  32,X'S) H   ( 321,X'S) 
RIDE C   (  33,X'S) H   ( 331,X'S) 
RIDE C   (  34,X'S) H   ( 341,X'S) 
RIDE C   (  35,X'S) H   ( 351,X'S) 
RIDE C   (  36,X'S) H   ( 361,X'S) 
RIDE C   (  38,X'S) H   ( 381,X'S) 
RIDE C   (  39,X'S) H   ( 391,X'S) 
RIDE C   (  40,X'S) H   ( 401,X'S) 
RIDE C   (  41,X'S) H   ( 411,X'S) 
RIDE C   (  42,X'S) H   ( 421,X'S) 
RIDE C   (  44,X'S) H   ( 441,X'S) H   ( 442,X'S) H   ( 443,X'S) 
RIDE C   (  46,X'S) H   ( 461,X'S) H   ( 462,X'S) H   ( 463,X'S) 
RIDE C   (  80,X'S) H   ( 801,X'S) 
RIDE C   (  82,X'S) H   ( 821,X'S) 
RIDE C   (  84,X'S) H   ( 841,X'S) 
RIDE C   (  88,X'S) H   ( 881,X'S) 
RIDE C   (  90,X'S) H   ( 901,X'S) 
RIDE C   (  92,X'S) H   ( 921,X'S) 
RIDE C   (  96,X'S) H   ( 961,X'S) 
RIDE C   (  98,X'S) H   ( 981,X'S) 
RIDE C   ( 100,X'S) H   (1001,X'S) 
RIDE C   ( 104,X'S) H   (1041,X'S) 
RIDE C   ( 106,X'S) H   (1061,X'S) 
RIDE C   ( 108,X'S) H   (1081,X'S) 
RIDE C   (  48,X'S) H   ( 481,X'S) 
RIDE C   (  50,X'S) H   ( 501,X'S) 
RIDE C   (  52,X'S) H   ( 521,X'S) 
RIDE C   (  56,X'S) H   ( 561,X'S) 
RIDE C   (  58,X'S) H   ( 581,X'S) 
RIDE C   (  60,X'S) H   ( 601,X'S) 
RIDE C   (  64,X'S) H   ( 641,X'S) 
RIDE C   (  66,X'S) H   ( 661,X'S) 
RIDE C   (  68,X'S) H   ( 681,X'S) 
RIDE C   (  72,X'S) H   ( 721,X'S) 
RIDE C   (  74,X'S) H   ( 741,X'S) 
RIDE C   (  76,X'S) H   ( 761,X'S) 
RIDE C   ( 111,X'S) H   (1111,X'S) H   (1112,X'S) 
RIDE C   ( 112,X'S) H   (1121,X'S) H   (1122,X'S) 
END                                                                             
;
_iucr_refine_instruction_details_restraints
;
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
REM   SHIFTLIMIT   START (DO NOT REMOVE THIS LINE) 
REM 
REM   SHIFTLIMIT   END (DO NOT REMOVE THIS LINE) 
REM   ASSEMBLY1   START (DO NOT REMOVE THIS LINE) 
REM   EXTERNAL BONDS 
DISTANCES  0.0 , 0.01  = MEAN 
CONTINUE C(54) TO C(51) C(154) TO C(51) 
REM   INTERNAL BONDS 
DISTANCES  0.0 , 0.01  = MEAN 
CONTINUE C(54) TO F(4) C(154) TO F(104) 
CONTINUE C(54) TO F(5) C(154) TO F(105) 
CONTINUE C(54) TO F(6) C(154) TO F(106) 
REM   ANGLES RESTRAINTS 
ANGLES  0.0 , 0.10  = MEAN 
CONTINUE F(4) TO C(54) TO C(51) F(104) TO C(154) TO C(51) 
CONTINUE F(5) TO C(54) TO C(51) F(105) TO C(154) TO C(51) 
CONTINUE F(5) TO C(54) TO F(4) F(105) TO C(154) TO F(104) 
CONTINUE F(6) TO C(54) TO C(51) F(106) TO C(154) TO C(51) 
CONTINUE F(6) TO C(54) TO F(4) F(106) TO C(154) TO F(104) 
CONTINUE F(6) TO C(54) TO F(5) F(106) TO C(154) TO F(105) 
REM   VIBRATIONAL RESTRAINTS 
VIBRATIONS 0.0, 0.0100  = 
CONTINUE C(54) TO C(51) C(154) TO C(51) 
CONTINUE C(54) TO F(4) C(154) TO F(104) 
CONTINUE C(54) TO F(5) C(154) TO F(105) 
CONTINUE C(54) TO F(6) C(154) TO F(106) 
VIBRATIONS 0.0, 0.00100  = 
CONTINUE C(54) TO C(154) 
CONTINUE F(4) TO F(104) 
CONTINUE F(5) TO F(105) 
CONTINUE F(6) TO F(106) 
REM   SIMILARITY RESTRAINTS 
U(IJ)'S 0.0, 0.0200  = 
CONTINUE C(54) TO C(51) C(154) TO C(51) 
CONTINUE C(54) TO F(4) C(154) TO F(104) 
CONTINUE C(54) TO F(5) C(154) TO F(105) 
CONTINUE C(54) TO F(6) C(154) TO F(106) 
U(IJ)'S 0.0, 0.00200  = 
CONTINUE C(54) TO C(154) 
CONTINUE F(4) TO F(104) 
CONTINUE F(5) TO F(105) 
CONTINUE F(6) TO F(106) 
REM   ASSEMBLY1   END (DO NOT REMOVE THIS LINE) 
REM   ASSEMBLY2   START (DO NOT REMOVE THIS LINE) 
REM   EXTERNAL BONDS 
DISTANCES  0.0 , 0.01  = MEAN 
CONTINUE C(70) TO C(67) C(170) TO C(67) 
REM   INTERNAL BONDS 
DISTANCES  0.0 , 0.01  = MEAN 
CONTINUE C(70) TO F(16) C(170) TO F(116) 
CONTINUE C(70) TO F(17) C(170) TO F(117) 
CONTINUE C(70) TO F(18) C(170) TO F(118) 
REM   ANGLES RESTRAINTS 
ANGLES  0.0 , 0.10  = MEAN 
CONTINUE F(16) TO C(70) TO C(67) F(116) TO C(170) TO C(67) 
CONTINUE F(17) TO C(70) TO C(67) F(117) TO C(170) TO C(67) 
CONTINUE F(17) TO C(70) TO F(16) F(117) TO C(170) TO F(116) 
CONTINUE F(18) TO C(70) TO C(67) F(118) TO C(170) TO C(67) 
CONTINUE F(18) TO C(70) TO F(16) F(118) TO C(170) TO F(116) 
CONTINUE F(18) TO C(70) TO F(17) F(118) TO C(170) TO F(117) 
REM   VIBRATIONAL RESTRAINTS 
VIBRATIONS 0.0, 0.0100  = 
CONTINUE C(70) TO C(67) C(170) TO C(67) 
CONTINUE C(70) TO F(16) C(170) TO F(116) 
CONTINUE C(70) TO F(17) C(170) TO F(117) 
CONTINUE C(70) TO F(18) C(170) TO F(118) 
VIBRATIONS 0.0, 0.00100  = 
CONTINUE C(70) TO C(170) 
CONTINUE F(16) TO F(116) 
CONTINUE F(17) TO F(117) 
CONTINUE F(18) TO F(118) 
REM   SIMILARITY RESTRAINTS 
U(IJ)'S 0.0, 0.0200  = 
CONTINUE C(70) TO C(67) C(170) TO C(67) 
CONTINUE C(70) TO F(16) C(170) TO F(116) 
CONTINUE C(70) TO F(17) C(170) TO F(117) 
CONTINUE C(70) TO F(18) C(170) TO F(118) 
U(IJ)'S 0.0, 0.00200  = 
CONTINUE C(70) TO C(170) 
CONTINUE F(16) TO F(116) 
CONTINUE F(17) TO F(117) 
CONTINUE F(18) TO F(118) 
REM   ASSEMBLY2   END (DO NOT REMOVE THIS LINE) 
END                                                                             
;