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_4120276
_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 H46 F24 Mn N2 O P4, C32 H12 B F24, C H2 Cl2'
_chemical_formula_sum            'C97 H60 B Cl2 F48 Mn N2 O P4'
_chemical_formula_weight         2442.00
_chemical_name_systematic        '[(P2N2)Mn(CO)(bppm)][BarF]'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-03-06
_audit_creation_method
;
  Olex2 1.2
  (compiled Nov  5 2012 18:25:38, GUI svn.r4372)
;
_cell_angle_alpha                106.131(2)
_cell_angle_beta                 93.897(2)
_cell_angle_gamma                92.643(2)
_cell_formula_units_Z            2
_cell_length_a                   12.5879(5)
_cell_length_b                   18.8382(7)
_cell_length_c                   22.7836(9)
_cell_measurement_reflns_used    9570
_cell_measurement_temperature    200.0
_cell_measurement_theta_max      30.284
_cell_measurement_theta_min      2.426
_cell_volume                     5166.1(4)
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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
;
XH, 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      200.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.986
_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  0.0325
_diffrn_reflns_av_unetI/netI     0.0404
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            108853
_diffrn_reflns_theta_full        30.58
_diffrn_reflns_theta_max         30.58
_diffrn_reflns_theta_min         1.65
_diffrn_source                   'microfocus sealed x-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.376
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6737
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0583 before and 0.0561 after correction.
The Ratio of minimum to maximum transmission is 0.9030.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear ? orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.570
_exptl_crystal_description       block
_exptl_crystal_F_000             2440
_exptl_crystal_preparation       'mounted in inert oil'
_exptl_crystal_recrystallization_method
'Crystallized from diffusion of pentane into methylene chloride solution.'
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.6
_exptl_crystal_size_min          0.4
_refine_diff_density_max         1.005
_refine_diff_density_min         -0.636
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1606
_refine_ls_number_reflns         31266
_refine_ls_number_restraints     95
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0882
_refine_ls_R_factor_gt           0.0597
_refine_ls_shift/su_max          0.017
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0811P)^2^+3.7707P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1547
_refine_ls_wR_factor_ref         0.1750
_reflns_number_gt                22255
_reflns_number_total             31266
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja405755j_si_003.cif
_cod_data_source_block           eh009_0m
_cod_original_cell_volume        5166.1(3)
_cod_database_code               4120276
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H70 of C70, H94 of C94, H54 of C54, H74 of C74, H86 of C86, H90 of C90,
  {H3a,H3b} of C3, H38 of C38, H62 of C62, {H2a,H2b} of C2, H30 of C30, {H6a,
  H6b} of C6, H24 of C24, H21 of C21, H44 of C44, H31 of C31, H50 of C50, H60
  of C60, H52 of C52, H92 of C92, H84 of C84, H27 of C27, H22 of C22, H12 of
  C12, H29 of C29, H16 of C16, H58 of C58, H23 of C23, H8 of C8, H76 of C76,
  H78 of C78, H36 of C36, H9 of C9, H18 of C18, H10 of C10, H19 of C19, H68 of
  C68, {H13a,H13b} of C13, H46 of C46, H28 of C28, H25 of C25, H42 of C42, H34
  of C34, H82 of C82, H15 of C15, {H32a,H32b} of C32, H66 of C66, {H4a,H4b} of
  C4, {H5a,H5b} of C5, H11 of C11, H17 of C17, {H97a,H97b} of C97, {H97c,H97d}
  of C97A
2. Restrained distances
 Cl1-Cl2
 2.86 with sigma of 0.02
 Cl1A-Cl2A
 2.86 with sigma of 0.02
 Cl1-C97 = Cl2-C97 = Cl1A-C97A = C97A-Cl2A
 1.7 with sigma of 0.02
 F22A-C63 ~ F22-C63 ~ F24A-C63 ~ F24-C63 ~ F23A-C63 ~ F23-C63
 with sigma of 0.01
 F13A-C47 ~ F15A-C47 ~ F14A-C47 ~ F15-C47 ~ F13-C47 ~ F14-C47
 with sigma of 0.02
 F15-F13A ~ F13-F14A ~ F14-F15A
 with sigma of 0.01
 F2A-C40 ~ F2-C40 ~ F1A-C40 ~ F1-C40 ~ F3-C40
 with sigma of 0.01
 F44-C79 ~ F43-C79
 with sigma of 0.02
 F48-C80 ~ F47A-C80 ~ F47-C80 ~ F46A-C80 ~ F46-C80 ~ F48A-C80
 with sigma of 0.02
 F35A-C95 ~ F35-C95 ~ F34A-C95 ~ F34-C95 ~ F36A-C95 ~ F36-C95
 with sigma of 0.01
 F18A-C48 ~ F17-C48 ~ F17A-C48 ~ F16-C48 ~ F16A-C48 ~ F18-C48
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(F24A) = Uanis(F23A) = Uanis(F22A)
Uanis(F41A) = Uanis(F41)
Uanis(F40A) = Uanis(F40)
Uanis(F42) = Uanis(F42A)
Uanis(F14A) = Uanis(F15)
Uanis(C97) = Uanis(C97A)
4. others
 Fixed Sof: F24(0.87) F22(0.87) F46(0.68) F17(0.55) F34(0.66) F21(0.55)
 F20(0.55) F47(0.68) F18(0.55) F23(0.87) F2(0.63) F1A(0.37) F1(0.63) F3A(0.37)
 F3(0.63) F2A(0.37) F13(0.76) F14A(0.24) F14(0.76) F15A(0.24) F15(0.76)
 F13A(0.24) F16(0.55) F19(0.55) F48(0.68) F35(0.66) F36(0.66) Cl1(0.36)
 C97(0.36) H97a(0.36) H97b(0.36) Cl2(0.36) F40(0.62) F41A(0.38) F42(0.62)
 F40A(0.38) F41(0.62) F42A(0.38) F19A(0.45) F20A(0.45) F21A(0.45) F23A(0.13)
 F24A(0.13) F22A(0.13) F16A(0.45) F17A(0.45) F18A(0.45) Cl2A(0.64) Cl1A(0.64)
 C97A(0.64) H97c(0.64) H97d(0.64) F47A(0.32) F48A(0.32) F46A(0.32) F36A(0.34)
 F35A(0.34) F34A(0.34)
5.a Secondary CH2 refined with riding coordinates:
 C32(H32a,H32b), C4(H4a,H4b), C5(H5a,H5b), C2(H2a,H2b), C3(H3a,H3b), C13(H13a,
 H13b), C6(H6a,H6b), C97(H97a,H97b), C97A(H97c,H97d)
5.b Aromatic/amide H refined with riding coordinates:
 C66(H66), C70(H70), C94(H94), C54(H54), C74(H74), C86(H86), C90(H90),
 C38(H38), C62(H62), C82(H82), C34(H34), C42(H42), C25(H25), C68(H68), C46(H46),
  C28(H28), C50(H50), C92(H92), C52(H52), C60(H60), C84(H84), C27(H27),
 C23(H23), C8(H8), C76(H76), C78(H78), C36(H36), C58(H58), C31(H31), C44(H44),
 C21(H21), C24(H24), C30(H30), C15(H15), C22(H22), C12(H12), C29(H29), C16(H16),
  C9(H9), C18(H18), C10(H10), C19(H19), C11(H11), C17(H17)
;