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_1517360
_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
'C56 H54 Mn N2 O P4, C32 H12 B F24, 0.72(C Cl2)'
_chemical_formula_sum            'C88.72 H66 B Cl1.44 F24 Mn N2 O P4'
_chemical_formula_weight         1872.75
_chemical_name_systematic        '[(P2N2)Mn(CO)(dppm)][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
_audit_creation_date             2013-12-11
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                73.339(2)
_cell_angle_beta                 83.858(2)
_cell_angle_gamma                89.798(2)
_cell_formula_units_Z            2
_cell_length_a                   10.1892(3)
_cell_length_b                   19.1512(7)
_cell_length_c                   22.8693(9)
_cell_measurement_reflns_used    9872
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.035
_cell_measurement_theta_min      2.269
_cell_volume                     4249.0(3)
_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
;
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.994
_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  0.0393
_diffrn_reflns_av_unetI/netI     0.0508
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            64380
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.222
_diffrn_reflns_theta_min         2.147
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.377
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9722
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0453 before and 0.0403 after correction.
The Ratio of minimum to maximum transmission is 0.9722.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.464
_exptl_crystal_description       block
_exptl_crystal_F_000             1902
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.135
_refine_diff_density_min         -1.019
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.126
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1154
_refine_ls_number_reflns         18848
_refine_ls_number_restraints     43
_refine_ls_restrained_S_all      1.133
_refine_ls_R_factor_all          0.0887
_refine_ls_R_factor_gt           0.0651
_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^)+(0.0335P)^2^+11.6749P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1405
_refine_ls_wR_factor_ref         0.1495
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14442
_reflns_number_total             18848
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4sc01801j2.cif
_cod_data_source_block           eh011_0m
_cod_depositor_comments
'Adding full bibliography for 1517360--1517366.cif.'
_cod_database_code               1517360
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 Cl4-C89 \\sim Cl3-C89 \\sim Cl1-C88 \\sim Cl2-C88
 with sigma of 0.02
 Cl1-Cl2 \\sim Cl4-Cl3
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Cl1) = Uanis(Cl2)
Uanis(Cl4) = Uanis(Cl3)
4. Others
 Fixed Sof: F22(0.54) F24(0.54) F23(0.54) Cl3(0.22) Cl4(0.22) C89(0.22)
 Cl2(0.5) Cl1(0.5) C88(0.5) F23A(0.46) F24A(0.46) F22A(0.46)
5.a Secondary CH2 refined with riding coordinates:
 C90(H90A,H90B), C5(H5A,H5B), C4(H4A,H4B), C3(H3A,H3B), C2(H2A,H2B), C13(H13A,
 H13B), C6(H6A,H6B)
5.b Aromatic/amide H refined with riding coordinates:
 C39(H39), C65(H65), C25(H25), C36(H36), C37(H37), C43(H43), C73(H73),
 C77(H77), C35(H35), C28(H28), C81(H81), C67(H67), C49(H49), C55(H55), C69(H69),
  C75(H75), C85(H85), C19(H19), C57(H57), C33(H33), C40(H40), C34(H34),
 C42(H42), C41(H41), C59(H59), C24(H24), C48(H48), C52(H52), C51(H51), C61(H61),
  C21(H21), C8(H8), C46(H46), C45(H45), C47(H47), C27(H27), C54(H54), C17(H17),
 C83(H83), C23(H23), C12(H12), C53(H53), C9(H9), C22(H22), C18(H18), C11(H11),
 C29(H29), C30(H30), C15(H15), C16(H16), C31(H31), C10(H10)
;
_shelx_hkl_checksum              32006
_shelx_res_checksum              58654
_shelxl_version_number           2013-2