Aryl Ether Cleavage by Group 9 and 10 Transition Metals: Stoichiometric Studies of Selectivity and Mechanism
Edouard, Guy A.; Kelley, Paul; Herbert, David E.; Agapie, Theodor; Organometallics  (2015) –; doi:10.1021/acs.organomet.5b00710

data_4086331
_publ_section_title
;
 Aryl Ether Cleavage by Group 9 and 10 Transition Metals: Stoichiometric
 Studies of Selectivity and Mechanism
;
_journal_name_full               Organometallics
_journal_paper_doi               10.1021/acs.organomet.5b00710
_journal_year                    2015
_chemical_formula_moiety         'C35 H48 Cl O P2 Rh, 0.5(C5 H12)'
_chemical_formula_sum            'C37.5 H54 Cl O P2 Rh'
_chemical_formula_weight         721.10
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_symmetry_space_group_name_Hall  'C -2yc'
_symmetry_space_group_name_H-M   'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-02-11
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 103.6640(10)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   26.5795(9)
_cell_length_b                   23.0419(8)
_cell_length_c                   24.1024(8)
_cell_measurement_reflns_used    9816
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      37.88
_cell_measurement_theta_min      2.37
_cell_volume                     14343.5(8)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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      100
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.956
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1043
_diffrn_reflns_av_unetI/netI     0.1301
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       47
_diffrn_reflns_limit_h_min       -47
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            383692
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.937
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         39.831
_diffrn_reflns_theta_min         2.253
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.668
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9249
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.1100 before and 0.0659 after correction.
The Ratio of minimum to maximum transmission is 0.9249.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.336
_exptl_crystal_description       plate
_exptl_crystal_F_000             6064
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.394
_refine_diff_density_min         -0.987
_refine_diff_density_rms         0.155
_refine_ls_abs_structure_details
;
 Flack x determined using 16934 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.439(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.009
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1579
_refine_ls_number_reflns         82412
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.009
_refine_ls_R_factor_all          0.1478
_refine_ls_R_factor_gt           0.0639
_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^)+(0.0300P)^2^+22.8750P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0915
_refine_ls_wR_factor_ref         0.1113
_reflns_Friedel_coverage         0.961
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.919
_reflns_number_gt                48320
_reflns_number_total             82412
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00710_si_001.cif
_cod_data_source_block           p15042_a
_cod_original_formula_sum        'C37.50 H54 Cl O P2 Rh'
_cod_database_code               4086331
_shelx_estimated_absorpt_t_max   0.961
_shelx_estimated_absorpt_t_min   0.856
_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.a Ternary CH refined with riding coordinates:
 C94(H9IA), C97(H6JA), C100(H3KA), C103(H0LA), C59(H1EA), C62(H8EA), C65(H5FA),
  C68(H2GA), C24(HT), C27(H0AA), C30(H7AA), C33(H4BA), C129(H129), C132(H132),
 C135(H135), C138(H138)
2.b Secondary CH2 refined with riding coordinates:
 C0AA(H7LA,H8LA), C3AA(H9LA,H0MA), C4AA(H1MA,H2MA), C03N(H5NA,H6NA), C042(H7NA,
 H8NA), C044(H9NA,H0OA)
2.c Aromatic/amide H refined with riding coordinates:
 C72(H9GA), C74(H0HA), C76(H1HA), C79(H2HA), C80(H3HA), C81(H4HA), C82(H5HA),
 C85(H6HA), C86(H7HA), C87(H8HA), C88(H9HA), C37(H1CA), C39(H2CA), C41(H3CA),
 C44(H4CA), C45(H5CA), C46(H6CA), C47(H7CA), C50(H8CA), C51(H9CA), C52(H0DA),
 C53(H1DA), C1(H), C3(HA), C5(HB), C8(HC), C9(HD), C10(HE), C11(HF), C14(HG),
 C15(HH), C16(HI), C17(HJ), C107(H107), C109(H109), C111(H111), C114(H114),
 C115(H115), C116(H116), C117(H117), C120(H120), C121(H121), C122(H122),
 C123(H123)
2.d Idealised Me refined as rotating group:
 C5AA(H3MA,H4MA,H5MA), C6AA(H6MA,H7MA,H8MA), C91(H0IA,H1IA,H2IA), C92(H3IA,
 H4IA,H5IA), C93(H6IA,H7IA,H8IA), C95(H0JA,H1JA,H2JA), C96(H3JA,H4JA,H5JA),
 C98(H7JA,H8JA,H9JA), C99(H0KA,H1KA,H2KA), C101(H4KA,H5KA,H6KA), C102(H7KA,H8KA,
 H9KA), C104(H1LA,H2LA,H3LA), C105(H4LA,H5LA,H6LA), C56(H2DA,H3DA,H4DA),
 C57(H5DA,H6DA,H7DA), C58(H8DA,H9DA,H0EA), C60(H2EA,H3EA,H4EA), C61(H5EA,H6EA,
 H7EA), C63(H9EA,H0FA,H1FA), C64(H2FA,H3FA,H4FA), C66(H6FA,H7FA,H8FA), C67(H9FA,
 H0GA,H1GA), C69(H3GA,H4GA,H5GA), C70(H6GA,H7GA,H8GA), C20(HK,HL,HM), C21(HN,HO,
 HP), C22(HQ,HR,HS), C25(HU,HV,HW), C26(HX,HY,HZ), C28(H1AA,H2AA,H3AA),
 C29(H4AA,H5AA,H6AA), C31(H8AA,H9AA,H0BA), C32(H1BA,H2BA,H3BA), C34(H5BA,H6BA,
 H7BA), C35(H8BA,H9BA,H0CA), C126(H12A,H12B,H12C), C127(H12D,H12E,H12F),
 C128(H12G,H12H,H12I), C130(H13A,H13B,H13C), C131(H13D,H13E,H13F), C133(H13G,
 H13H,H13I), C134(H13J,H13K,H13L), C136(H13M,H13N,H13O), C137(H13P,H13Q,H13R),
 C139(H13S,H13T,H13U), C140(H14A,H14B,H14C), C03C(H9MA,H0NA,H1NA), C03I(H2NA,
 H3NA,H4NA)
;
_shelx_res_checksum              86973
_shelx_hkl_checksum              69228
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'