Synthesis of a Tris(phosphaalkene)phosphine Ligand and Fundamental Organometallic Reactions on Its Sterically Shielded Metal Complexes
Miura-Akagi, Preston M.; Nakashige, Mika L.; Maile, Caitlin K.; Oshiro, Shelly M.; Gurr, Joshua R.; Yoshida, Wesley Y.; Royappa, A. Timothy; Krause, Colleen E.; Rheingold, Arnold L.; Hughes, Russell P.; Cain, Matthew F.; Organometallics 35 (2016) 2224–; doi:10.1021/acs.organomet.6b00250

data_4086585
_publ_contact_author_name
;
;
_publ_section_title
;
 Synthesis of a Tris(phosphaalkene)phosphine Ligand and Fundamental
 Organometallic Reactions on Its Sterically Shielded Metal Complexes
;
_journal_issue                   13
_journal_name_full               Organometallics
_journal_page_first              2224
_journal_paper_doi               10.1021/acs.organomet.6b00250
_journal_volume                  35
_journal_year                    2016
_chemical_formula_moiety         'C75 H102 Cl P4 Rh, C H Cl3'
_chemical_formula_sum            'C76 H103 Cl4 P4 Rh'
_chemical_formula_weight         1385.17
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3'
_symmetry_space_group_name_Hall  '-R 3'
_symmetry_space_group_name_H-M   'R -3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2016-05-03
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   31.949(3)
_cell_length_b                   31.949(3)
_cell_length_c                   42.298(4)
_cell_measurement_reflns_used    3600
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.95
_cell_measurement_theta_min      2.21
_cell_volume                     37391(6)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XM (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.968
_diffrn_measured_fraction_theta_max 0.968
_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  0.0715
_diffrn_reflns_av_unetI/netI     0.1078
_diffrn_reflns_Laue_measured_fraction_full 0.968
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_number            23642
_diffrn_reflns_point_group_measured_fraction_full 0.968
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         1.549
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.447
_exptl_absorpt_correction_T_max  0.203
_exptl_absorpt_correction_T_min  0.156
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.107
_exptl_crystal_description       block
_exptl_crystal_F_000             13176
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.23
_refine_diff_density_max         0.817
_refine_diff_density_min         -0.736
_refine_diff_density_rms         0.088
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.914
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     824
_refine_ls_number_reflns         14169
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      0.917
_refine_ls_R_factor_all          0.0944
_refine_ls_R_factor_gt           0.0544
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0433P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1206
_refine_ls_wR_factor_ref         0.1414
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                7759
_reflns_number_total             14169
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00250_si_004.cif
_cod_data_source_block           cain07_sq
_cod_original_cell_volume        37391(8)
_cod_database_code               4086585
_shelx_estimated_absorpt_t_max   0.904
_shelx_estimated_absorpt_t_min   0.878
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid body (RIGU) restrains
 C16, C16A, C17, C17A, C18, C18A, C15
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
3. Others
 Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C17A)=Sof(H17D)=Sof(H17E)=
 Sof(H17F)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=1-FVAR(1)
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C81(H81)
4.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C5(H5), C21(H21), C23(H23), C37(H37), C39(H39), C56(H56), C57(H57),
 C58(H58), C59(H59), C61(H61), C63(H63), C64(H64), C65(H65), C66(H66), C68(H68),
  C70(H70), C71(H71), C72(H72), C73(H73), C75(H75)
4.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C18(H18A,H18B,H18C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,
 H28B,H28C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C),
 C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C44(H44A,H44B,
 H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C48(H48A,H48B,H48C), C49(H49A,
 H49B,H49C), C50(H50A,H50B,H50C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C),
 C54(H54A,H54B,H54C), C16A(H16D,H16E,H16F), C17A(H17D,H17E,H17F), C18A(H18D,
 H18E,H18F)
;
_shelx_res_checksum              94861
_shelx_hkl_checksum              67717
_shelx_fab_checksum              88540
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'