Rapid, Reversible Heterolytic Cleavage of Bound H2
Elliott B. Hulley; Kevin D. Welch; Aaron M. Appel; Daniel L. DuBois; R. Morris Bullock; Journal of the American Chemical Society 135 (2013) 11736–11739; doi:10.1021/ja405755j

data_4120277
_publ_section_title
;
 Rapid, Reversible Heterolytic Cleavage of Bound H2
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11736
_journal_page_last               11739
_journal_paper_doi               10.1021/ja405755j
_journal_volume                  135
_journal_year                    2013
_chemical_formula_moiety
;
C64 H48 F24 Mn N2 O P4, C32 H12 B F24, 1.35(C H2 Cl2), 
C0.64 H1.27 Cl1.31, C0.17 Cl0.34
;
_chemical_formula_sum            'C98.15 H63.96 B Cl4.34 F48 Mn N2 O P4'
_chemical_formula_weight         2542.98
_chemical_name_systematic        endo-(P2N2H)MnH(CO)(bppm)[BArF]
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2013-06-06
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.8010(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.3703(4)
_cell_length_b                   15.5253(4)
_cell_length_c                   41.7760(10)
_cell_measurement_reflns_used    9988
_cell_measurement_temperature    150(1)
_cell_measurement_theta_max      26.17
_cell_measurement_theta_min      2.38
_cell_volume                     10429.4(4)
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
XS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      150(1)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.963
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0313
_diffrn_reflns_av_unetI/netI     0.0470
_diffrn_reflns_Laue_measured_fraction_full 0.963
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       49
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_number            45805
_diffrn_reflns_point_group_measured_fraction_full 0.963
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.040
_diffrn_reflns_theta_min         1.749
_diffrn_source                   'microfocus sealed x-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.434
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.620
_exptl_crystal_description       block
_exptl_crystal_F_000             5083
_exptl_crystal_preparation       'placed in oil'
_exptl_crystal_recrystallization_method 'from CH2Cl2/pentane at 1.4 atm H2'
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.34
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.690
_refine_diff_density_min         -0.794
_refine_diff_density_rms         0.086
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.108
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1547
_refine_ls_number_reflns         18188
_refine_ls_number_restraints     44
_refine_ls_restrained_S_all      1.107
_refine_ls_R_factor_all          0.0960
_refine_ls_R_factor_gt           0.0743
_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^)+(0.0563P)^2^+45.1190P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1764
_refine_ls_wR_factor_ref         0.1866
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14002
_reflns_number_total             18188
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja405755j_si_004.cif
_cod_data_source_block           eh010_0m_weak
_cod_database_code               4120277
_olex2_refinement_description
;
1. others
 Fixed Sof: F29(0.6952) F30(0.6952) F(0.6952) H75A(0.3462) H75(0.6538)
 C45B(0.3462) H45A(0.3462) H45B(0.3462) C46A(0.6538) C47A(0.6538) H47A(0.6538)
 C48A(0.6538) H48A(0.6538) C49A(0.6538) H49A(0.6538) C50A(0.6538) H50A(0.6538)
 C51A(0.6538) H51A(0.6538) Cl1(0.3462) Cl3(0.3462) C52B(0.3462) H52C(0.3462)
 H52D(0.3462) C50B(0.3462) H50B(0.3462) C51B(0.3462) H51B(0.3462) C46B(0.3462)
 C47B(0.3462) H47B(0.3462) C48B(0.3462) H48B(0.3462) C49B(0.3462) H49B(0.3462)
 Cl(0.6538) C52A(0.6357) H52A(0.6357) H52B(0.6357) C45A(0.6538) H45C(0.6538)
 H45D(0.6538) Cl0A(0.6538) F2AA(0.3048) F1AA(0.3048) F0AA(0.3048)
 Fixed Uiso: H55(0.062) H97A(0.1) H97B(0.1) H86(0.036) H66(0.042) H76(0.032)
 H74(0.036) H82(0.036) H84(0.043) H90(0.043) H92(0.044) H94(0.033) H68(0.047)
 H70(0.039) H78(0.031) H31(0.03) H29(0.051) H27(0.045) H2A(0.022) H2B(0.022)
 H45(0.027) H6(0.033) H4(0.026) H11(0.028) H13(0.04) H15(0.027) H23(0.042)
 H21(0.04) H19(0.03) H60(0.037) H61(0.05) H62(0.049) H63(0.047) H64(0.038)
 H37A(0.035) H37B(0.035) H75A(0.034) H75(0.034) H45A(0.042) H45B(0.042)
 H36A(0.032) H36B(0.032) H35A(0.027) H35B(0.027) H34A(0.027) H34B(0.027)
 H38A(0.034) H38B(0.034) H44(0.036) H43(0.042) H42(0.052) H41(0.058) H40(0.047)
 H58(0.043) H57(0.062) H56(0.064) H54(0.045) H47A(0.053) H48A(0.089)
 H49A(0.073) H50A(0.089) H51A(0.051) H52C(0.095) H52D(0.095) H50B(0.073)
 H51B(0.065) H47B(0.056) H48B(0.073) H49B(0.095) H52A(0.073) H52B(0.073)
 H45C(0.042) H45D(0.042)
 Fixed X: H55(0.7252) H97A(0.1341) H97B(0.142) H86(-0.0091) H66(0.1785) H76(-
 0.0222) H74(0.141) H82(0.0242) H84(-0.0711) H90(0.1406) H92(-0.0431) H94(-
 0.0944) H68(0.3889) H70(0.1702) H78(-0.0849) H31(0.4278) H29(0.6481)
 H27(0.6301) H2A(0.3602) H2B(0.3379) H45(0.1241) H6(-0.0217) H4(0.2288)
 H11(0.2411) H13(0.2354) H15(0.3018) H23(0.5206) H21(0.6161) H19(0.5054)
 H60(0.2156) H61(0.0715) H62(-0.0197) H63(0.0292) H64(0.1712) H37A(0.3279)
 H37B(0.3716) H75A(0.4434) H75(0.4396) H45A(0.4379) H45B(0.5316) H36A(0.5147)
 H36B(0.569) H35A(0.4479) H35B(0.5206) H34A(0.2826) H34B(0.3083) H38A(0.4618)
 H38B(0.3783) H44(0.2661) H43(0.1921) H42(0.2381) H41(0.3572) H40(0.4311)
 H58(0.6254) H57(0.7565) H56(0.8049) H54(0.5958) H47A(0.4952) H48A(0.6164)
 H49A(0.7439) H50A(0.7501) H51A(0.6288) H52C(0.7258) H52D(0.7312) H50B(0.3902)
 H51B(0.3749) H47B(0.6107) H48B(0.626) H49B(0.5158) H52A(0.5682) H52B(0.5171)
 H45C(0.4278) H45D(0.483)
 Fixed Y: H55(0.2061) H97A(0.3445) H97B(0.3104) H86(0.5086) H66(0.4833)
 H76(0.6366) H74(0.6336) H82(0.3912) H84(0.2579) H90(0.6995) H92(0.8286)
 H94(0.6094) H68(0.485) H70(0.5627) H78(0.5265) H31(0.6357) H29(0.7612)
 H27(0.528) H2A(0.5922) H2B(0.5051) H45(0.5329) H6(0.4138) H4(0.3924)
 H11(0.6649) H13(0.7843) H15(0.5337) H23(0.5701) H21(0.3922) H19(0.3172)
 H60(0.4293) H61(0.4516) H62(0.3703) H63(0.2686) H64(0.2457) H37A(0.3575)
 H37B(0.2655) H75A(0.4234) H75(0.4154) H45A(0.4205) H45B(0.4126) H36A(0.2553)
 H36B(0.3401) H35A(0.1727) H35B(0.1545) H34A(0.1702) H34B(0.1822) H38A(0.045)
 H38B(0.0433) H44(-0.0253) H43(-0.0736) H42(-0.0372) H41(0.045) H40(0.0922)
 H58(0.425) H57(0.4369) H56(0.3264) H54(0.1908) H47A(0.5622) H48A(0.6426)
 H49A(0.5919) H50A(0.4607) H51A(0.3803) H52C(0.6077) H52D(0.5151) H50B(0.1873)
 H51B(0.3096) H47B(0.2797) H48B(0.1574) H49B(0.1111) H52A(0.1741) H52B(0.0981)
 H45C(0.4502) H45D(0.3685)
 Fixed Z: H55(0.8235) H97A(0.5446) H97B(0.5812) H86(0.5512) H66(0.6652)
 H76(0.7318) H74(0.6703) H82(0.6386) H84(0.5567) H90(0.597) H92(0.5381)
 H94(0.5824) H68(0.6276) H70(0.5731) H78(0.6425) H31(0.8504) H29(0.8678)
 H27(0.8248) H2A(0.795) H2B(0.7735) H45(0.8309) H6(0.7553) H4(0.7678)
 H11(0.8079) H13(0.8937) H15(0.8924) H23(0.7686) H21(0.7154) H19(0.7898)
 H60(0.9103) H61(0.9044) H62(0.8674) H63(0.8356) H64(0.8406) H37A(0.9341)
 H37B(0.9326) H75A(0.9156) H75(0.9112) H45A(0.9704) H45B(0.9656) H36A(0.9261)
 H36B(0.9236) H35A(0.8444) H35B(0.875) H34A(0.8853) H34B(0.8504) H38A(0.8949)
 H38B(0.8679) H44(0.8838) H43(0.923) H42(0.9773) H41(0.9925) H40(0.9535)
 H58(0.8814) H57(0.8671) H56(0.838) H54(0.8387) H47A(0.9327) H48A(0.9335)
 H49A(0.9622) H50A(0.9902) H51A(0.9894) H52C(0.953) H52D(0.9364) H50B(1.0304)
 H51B(0.9972) H47B(0.9821) H48B(1.0154) H49B(1.0395) H52A(1.0458) H52B(1.0251)
 H45C(0.9636) H45D(0.9776)
;
_shelx_estimated_absorpt_t_max   0.938
_shelx_estimated_absorpt_t_min   0.859
_shelx_res_checksum              12291
_shelxl_version_number           2013-2