Heterolytic cleavage of H2by bifunctional manganese(i) complexes: impact of ligand dynamics, electrophilicity, and base positioning
Hulley, Elliott B.; Helm, Monte L.; Bullock, R. Morris; Chem. Sci. 5 (2014) 4729–; doi:10.1039/C4SC01801J

data_1517364
_publ_section_title
;
 Heterolytic cleavage of H2by bifunctional manganese(i) complexes: impact
 of ligand dynamics, electrophilicity, and base positioning
;
_journal_issue                   12
_journal_name_full               'Chem. Sci.'
_journal_page_first              4729
_journal_paper_doi               10.1039/C4SC01801J
_journal_volume                  5
_journal_year                    2014
_chemical_formula_moiety
'C61 H41 F24 Mn N O P4, C24 B F20, 2(C6 H5 F), C6 H6'
_chemical_formula_sum            'C103 H57 B F46 Mn N O P4'
_chemical_formula_weight         2388.12
_chemical_name_systematic        '[(Ph,Me-PNP)Mn(CO(bppm)][B(C6F5)4]'
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_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
_audit_creation_date             2013-12-12
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_cell_angle_alpha                108.7140(10)
_cell_angle_beta                 109.9690(10)
_cell_angle_gamma                96.4910(10)
_cell_formula_units_Z            1
_cell_length_a                   13.8260(5)
_cell_length_b                   14.0301(5)
_cell_length_c                   14.8023(5)
_cell_measurement_reflns_used    9810
_cell_measurement_temperature    150
_cell_measurement_theta_max      28.678
_cell_measurement_theta_min      2.499
_cell_volume                     2474.82(15)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_temperature      150
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0177
_diffrn_reflns_av_unetI/netI     0.0360
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            44168
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.856
_diffrn_reflns_theta_min         1.583
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.336
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6803
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0498 before and 0.0424 after correction.
The Ratio of minimum to maximum transmission is 0.9122.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear dark blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.602
_exptl_crystal_description       block
_exptl_crystal_F_000             1194
_exptl_crystal_preparation       'placed in oil'
_exptl_crystal_recrystallization_method 'crystallized from fluorobenzene'
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.791
_refine_diff_density_min         -0.424
_refine_diff_density_rms         0.060
_refine_ls_abs_structure_details
;
 Flack x determined using 8853 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.006(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1430
_refine_ls_number_reflns         22509
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0491
_refine_ls_R_factor_gt           0.0420
_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^)+(0.0824P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1123
_refine_ls_wR_factor_ref         0.1174
_reflns_Friedel_coverage         0.924
_reflns_Friedel_fraction_full    0.953
_reflns_Friedel_fraction_max     0.917
_reflns_number_gt                20011
_reflns_number_total             22509
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4sc01801j2.cif
_cod_data_source_block           eh022_0m
_cod_depositor_comments
'Adding full bibliography for 1517360--1517366.cif.'
_cod_database_code               1517364
_shelxl_version_number           2013-2
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Fixed Sof: C98A(0.47) H98A(0.47) C93A(0.47) C94A(0.47) H94A(0.47) C95A(0.47)
 H95A(0.47) C96A(0.47) H96A(0.47) C97A(0.47) H97A(0.47) C92(0.53) C93(0.53)
 H93(0.53) C94(0.53) H94(0.53) C1H(0.53) H1H(0.53) C1A(0.53) H1A(0.53)
 C1B(0.53) H1B(0.53) F46(0.47) F46A(0.53)
3.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C29(H29A,H29B), C2(H2A,H2B)
3.b Aromatic/amide H refined with riding coordinates:
 C43(H43), C16(H16), C47(H47), C31(H31), C49(H49), C35(H35), C33(H33), C6(H6),
 C28(H28), C51(H51), C19(H19), C20(H20), C10(H10), C55(H55), C21(H21), C27(H27),
  C39(H39), C18(H18), C9(H9), C25(H25), C57(H57), C8(H8), C12(H12), C7(H7),
 C22(H22), C59(H59), C41(H41), C24(H24), C13(H13), C15(H15), C14(H14), C26(H26),
  C89(H89), C90(H90), C91(H91), C87(H87), C88(H88), C98A(H98A), C94A(H94A),
 C95A(H95A), C96A(H96A), C97A(H97A), C97(H97), C98(H98), C99(H99), C100(H100),
 C101(H101), C96(H96), C93(H93), C94(H94), C1H(H1H), C1A(H1A), C1B(H1B)
3.c Fitted hexagon refined as free rotating group:
 C89(C90,C91,C86,C87,C88), C98A(C93A,C94A,C95A,C96A,C97A), C97(C98,C99,C100,
 C101,C96), C92(C93,C94,C1H,C1A,C1B)
3.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C)
;
_shelx_res_checksum              53769
_shelx_hkl_checksum              392