Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2002 data_1 _database_code_CSD 189436 _journal_coden_Cambridge 186 loop_ _publ_author_name 'Cole-Hamilton, David' 'Foster, Douglas F.' 'Haxton, Katherine J.' 'Morris, Russell E.' 'Ropartz, Loic' 'Slawin, Alexandra M. Z.' _publ_contact_author_name 'Prof David Cole-Hamilton' _publ_contact_author_address ; Department of Chemistry University of St. Andrews St. Andrews United Kingdom Ky16 9ST ; _publ_contact_author_email 'DJC@ST-AND.AC.UK' _publ_requested_journal 'Dalton Transactions' _publ_section_title ; Phosphine containing dendrimers for highly regioselective rhodium catalysed hydroformylation of 1-octene. A positve dendritic effect ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C56 H56 P4 Si' _chemical_formula_sum 'C56 H56 P4 Si' _chemical_formula_weight 880.98 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Si' 'Si' 0.0817 0.0704 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'P' 'P' 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M I-4 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' 'y, -x, -z' '-y, x, -z' 'x+1/2, y+1/2, z+1/2' '-x+1/2, -y+1/2, z+1/2' 'y+1/2, -x+1/2, -z+1/2' '-y+1/2, x+1/2, -z+1/2' _cell_length_a 20.4806(14) _cell_length_b 20.4806(14) _cell_length_c 5.7429(6) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2408.9(3) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 85 _cell_measurement_theta_min 12 _cell_measurement_theta_max 168 _exptl_crystal_description prism _exptl_crystal_colour colourles _exptl_crystal_size_max .18 _exptl_crystal_size_mid .1 _exptl_crystal_size_min .1 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.215 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 932 _exptl_absorpt_coefficient_mu 0.218 _exptl_absorpt_correction_type sadabs _exptl_absorpt_correction_T_min 0.761556 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean 0.9 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6048 _diffrn_reflns_av_R_equivalents 0.1057 _diffrn_reflns_av_sigmaI/netI 0.1213 _diffrn_reflns_limit_h_min -22 _diffrn_reflns_limit_h_max 22 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min -6 _diffrn_reflns_limit_l_max 6 _diffrn_reflns_theta_min 2.81 _diffrn_reflns_theta_max 23.31 _reflns_number_total 1725 _reflns_number_gt 1090 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0100P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0006(2) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.01(13) _refine_ls_number_reflns 1725 _refine_ls_number_parameters 139 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0951 _refine_ls_R_factor_gt 0.0453 _refine_ls_wR_factor_ref 0.0599 _refine_ls_wR_factor_gt 0.0512 _refine_ls_goodness_of_fit_ref 0.821 _refine_ls_restrained_S_all 0.821 _refine_ls_shift/su_max 0.003 _refine_ls_shift/su_mean 0.001 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Si1 Si 0.0000 0.0000 0.0000 0.0403(6) Uani 1 4 d S . . C1 C -0.06894(14) 0.02083(14) 0.1994(6) 0.0432(9) Uani 1 1 d . . . H1A H -0.0680 -0.0098 0.3280 0.052 Uiso 1 1 calc R . . H1B H -0.0604 0.0638 0.2637 0.052 Uiso 1 1 calc R . . C2 C -0.13909(16) 0.02121(16) 0.0993(6) 0.0438(11) Uani 1 1 d . . . H2A H -0.1517 -0.0228 0.0559 0.053 Uiso 1 1 calc R . . H2B H -0.1407 0.0483 -0.0391 0.053 Uiso 1 1 calc R . . P1 P -0.19617(4) 0.05321(5) 0.3197(2) 0.0466(3) Uani 1 1 d . . . C3 C -0.27487(15) 0.04962(16) 0.1698(7) 0.0454(9) Uani 1 1 d . . . C4 C -0.28622(18) 0.01922(18) -0.0384(8) 0.0610(11) Uani 1 1 d . . . H4A H -0.2514 0.0005 -0.1181 0.073 Uiso 1 1 calc R . . C5 C -0.3479(2) 0.01563(19) -0.1327(8) 0.0751(14) Uani 1 1 d . . . H5A H -0.3547 -0.0064 -0.2722 0.090 Uiso 1 1 calc R . . C6 C -0.3998(2) 0.0450(2) -0.0192(11) 0.0827(16) Uani 1 1 d . . . H6A H -0.4415 0.0432 -0.0831 0.099 Uiso 1 1 calc R . . C7 C -0.3897(2) 0.0765(2) 0.1855(11) 0.0788(15) Uani 1 1 d . . . H7A H -0.4244 0.0965 0.2617 0.095 Uiso 1 1 calc R . . C8 C -0.3279(2) 0.07882(16) 0.2803(8) 0.0701(13) Uani 1 1 d . . . H8A H -0.3215 0.1003 0.4211 0.084 Uiso 1 1 calc R . . C9 C -0.17832(16) 0.14055(16) 0.3003(7) 0.0422(9) Uani 1 1 d . . . C10 C -0.19723(16) 0.1797(2) 0.1144(7) 0.0593(12) Uani 1 1 d . . . H10A H -0.2199 0.1611 -0.0091 0.071 Uiso 1 1 calc R . . C11 C -0.1832(2) 0.2452(2) 0.1091(7) 0.0668(14) Uani 1 1 d . . . H11A H -0.1973 0.2704 -0.0160 0.080 Uiso 1 1 calc R . . C12 C -0.1490(2) 0.2737(2) 0.2846(11) 0.0739(16) Uani 1 1 d . . . H12A H -0.1396 0.3181 0.2802 0.089 Uiso 1 1 calc R . . C13 C -0.12873(19) 0.2363(2) 0.4671(9) 0.0750(13) Uani 1 1 d . . . H13A H -0.1047 0.2555 0.5864 0.090 Uiso 1 1 calc R . . C14 C -0.14326(17) 0.1704(2) 0.4783(8) 0.0588(12) Uani 1 1 d . . . H14A H -0.1295 0.1459 0.6055 0.071 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Si1 0.0366(8) 0.0366(8) 0.0477(15) 0.000 0.000 0.000 C1 0.035(2) 0.046(2) 0.049(2) 0.007(2) 0.001(2) 0.0037(16) C2 0.048(3) 0.037(2) 0.046(3) -0.0005(18) -0.0002(19) -0.0006(17) P1 0.0403(7) 0.0490(7) 0.0504(6) 0.0019(7) 0.0057(6) 0.0042(6) C3 0.036(2) 0.044(2) 0.056(3) 0.006(2) 0.014(3) -0.0025(18) C4 0.040(3) 0.071(3) 0.072(3) -0.005(3) 0.004(2) 0.002(2) C5 0.059(3) 0.071(3) 0.095(4) -0.001(3) -0.019(3) -0.010(3) C6 0.047(3) 0.059(4) 0.141(6) 0.021(4) -0.032(4) -0.007(3) C7 0.041(3) 0.056(3) 0.139(5) 0.003(4) 0.020(4) -0.001(2) C8 0.047(3) 0.064(3) 0.099(4) 0.002(3) 0.010(3) 0.005(2) C9 0.041(2) 0.047(3) 0.038(2) -0.005(2) 0.004(2) 0.0072(19) C10 0.058(3) 0.054(3) 0.066(4) -0.003(2) -0.001(2) -0.008(2) C11 0.076(3) 0.053(3) 0.071(4) 0.011(2) 0.000(3) -0.003(2) C12 0.069(3) 0.048(3) 0.105(5) -0.007(3) 0.000(3) -0.003(3) C13 0.063(3) 0.070(4) 0.092(4) -0.033(3) -0.010(3) -0.005(3) C14 0.056(3) 0.053(3) 0.067(3) -0.008(3) -0.013(3) 0.013(2) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Si1 C1 1.867(3) . ? Si1 C1 1.867(3) 2 ? Si1 C1 1.867(3) 3 ? Si1 C1 1.867(3) 4 ? C1 C2 1.547(4) . ? C2 P1 1.844(3) . ? P1 C9 1.829(3) . ? P1 C3 1.829(3) . ? C3 C4 1.368(5) . ? C3 C8 1.393(4) . ? C4 C5 1.377(5) . ? C5 C6 1.384(5) . ? C6 C7 1.357(6) . ? C7 C8 1.379(5) . ? C9 C10 1.390(5) . ? C9 C14 1.390(5) . ? C10 C11 1.372(4) . ? C11 C12 1.359(5) . ? C12 C13 1.363(6) . ? C13 C14 1.385(4) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C1 Si1 C1 104.4(2) . 2 ? C1 Si1 C1 112.09(11) . 3 ? C1 Si1 C1 112.09(11) 2 3 ? C1 Si1 C1 112.09(11) . 4 ? C1 Si1 C1 112.09(11) 2 4 ? C1 Si1 C1 104.4(2) 3 4 ? C2 C1 Si1 118.4(2) . . ? C1 C2 P1 109.6(2) . . ? C9 P1 C3 100.75(15) . . ? C9 P1 C2 100.32(16) . . ? C3 P1 C2 102.79(18) . . ? C4 C3 C8 117.5(3) . . ? C4 C3 P1 125.4(3) . . ? C8 C3 P1 117.1(3) . . ? C3 C4 C5 121.6(4) . . ? C4 C5 C6 119.7(4) . . ? C7 C6 C5 119.9(4) . . ? C6 C7 C8 119.9(4) . . ? C7 C8 C3 121.4(4) . . ? C10 C9 C14 117.0(4) . . ? C10 C9 P1 123.7(3) . . ? C14 C9 P1 119.2(3) . . ? C11 C10 C9 121.5(4) . . ? C12 C11 C10 120.7(4) . . ? C11 C12 C13 119.1(4) . . ? C12 C13 C14 121.2(4) . . ? C13 C14 C9 120.4(4) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C1 Si1 C1 C2 -162.6(3) 2 . . . ? C1 Si1 C1 C2 75.9(3) 3 . . . ? C1 Si1 C1 C2 -41.0(3) 4 . . . ? Si1 C1 C2 P1 -172.83(16) . . . . ? C1 C2 P1 C9 76.4(2) . . . . ? C1 C2 P1 C3 -180.0(2) . . . . ? C9 P1 C3 C4 113.4(3) . . . . ? C2 P1 C3 C4 10.1(3) . . . . ? C9 P1 C3 C8 -68.4(3) . . . . ? C2 P1 C3 C8 -171.7(3) . . . . ? C8 C3 C4 C5 -2.0(5) . . . . ? P1 C3 C4 C5 176.2(3) . . . . ? C3 C4 C5 C6 2.0(6) . . . . ? C4 C5 C6 C7 -0.7(7) . . . . ? C5 C6 C7 C8 -0.4(7) . . . . ? C6 C7 C8 C3 0.4(6) . . . . ? C4 C3 C8 C7 0.8(5) . . . . ? P1 C3 C8 C7 -177.5(3) . . . . ? C3 P1 C9 C10 -32.7(3) . . . . ? C2 P1 C9 C10 72.6(3) . . . . ? C3 P1 C9 C14 148.1(3) . . . . ? C2 P1 C9 C14 -106.6(3) . . . . ? C14 C9 C10 C11 -1.4(5) . . . . ? P1 C9 C10 C11 179.3(3) . . . . ? C9 C10 C11 C12 1.3(6) . . . . ? C10 C11 C12 C13 0.0(6) . . . . ? C11 C12 C13 C14 -1.1(7) . . . . ? C12 C13 C14 C9 0.9(6) . . . . ? C10 C9 C14 C13 0.3(5) . . . . ? P1 C9 C14 C13 179.6(3) . . . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 23.31 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.162 _refine_diff_density_min -0.172 _refine_diff_density_rms 0.038