# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is © The Royal Society of Chemistry 2005 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _publ_contact_author_name 'ProfD Koichiro Oshima' _publ_contact_author_address ; Department of Material Chemistry Kyoto University Kyoto-daigaku Katsura Nishikyo Kyoto 615-8510 JAPAN ; _publ_contact_author_email OSHIMA@ORGRXN.MBOX.MEDIA.KYOTO-U.AC.JP _publ_section_title ; A new method for the synthesis of acyltitanium complexes and their application to copper-mediated acylmetallation of carbon-carbon multiple bonds in aqueous media ; loop_ _publ_author_name 'Koichiro Oshima' 'Takuma Fujioka' 'Zhenfu Han' 'Hiroshi Shinokubo' 'Shin-ichi Usugi' 'Hideki Yorimitsu' data_k:\crystals\obc\proper\b503117f _database_code_depnum_ccdc_archive 'CCDC 265208' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common 'bis(cyclopentadienyl)-p-toluoyltitanium bromide' _chemical_melting_point ? _chemical_formula_moiety 'C18 H17 Br O Ti' _chemical_formula_sum 'C18 H17 Br O Ti' _chemical_formula_weight 377.13 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' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.7237(7) _cell_length_b 9.8885(9) _cell_length_c 11.0929(10) _cell_angle_alpha 81.444(2) _cell_angle_beta 70.937(2) _cell_angle_gamma 89.529(2) _cell_volume 791.12(12) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description block _exptl_crystal_colour orange _exptl_crystal_size_max 0.4 _exptl_crystal_size_mid 0.36 _exptl_crystal_size_min 0.2 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.583 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 380 _exptl_absorpt_coefficient_mu 3.062 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _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 ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean 8.366 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4848 _diffrn_reflns_av_R_equivalents 0.0125 _diffrn_reflns_av_sigmaI/netI 0.0180 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 7 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 1.97 _diffrn_reflns_theta_max 28.36 _reflns_number_total 3431 _reflns_number_gt 2791 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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 [1.00000+0.00000exp(0.00(sin\q/\l)^2^)]/ [\s^2^(Fo^2^)+0.0000+0.1377*P+(0.0626P)^2^+0.0000sin\q/\l] where P = 0.00000Fo^2^ + 1.00000Fc^2^ ; _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3431 _refine_ls_number_parameters 191 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0417 _refine_ls_R_factor_gt 0.0335 _refine_ls_wR_factor_ref 0.0926 _refine_ls_wR_factor_gt 0.0892 _refine_ls_goodness_of_fit_ref 0.980 _refine_ls_restrained_S_all 0.980 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 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 Br1 Br 0.73802(3) 0.30384(3) 0.86598(3) 0.06638(13) Uani 1 1 d . . . Ti1 Ti 0.40126(5) 0.28262(4) 0.84665(4) 0.03817(11) Uani 1 1 d . . . O1 O 0.5332(2) 0.11204(19) 0.75489(18) 0.0582(4) Uani 1 1 d . . . C1 C 0.1028(4) 0.0500(3) 0.7083(2) 0.0522(6) Uani 1 1 d . . . H1 H 0.0452 0.1272 0.7383 0.063 Uiso 1 1 calc R . . C2 C 0.0114(4) -0.0406(3) 0.6645(2) 0.0575(6) Uani 1 1 d . . . H2 H -0.1068 -0.0231 0.6639 0.069 Uiso 1 1 calc R . . C3 C 0.0939(4) -0.1576(3) 0.6214(2) 0.0581(6) Uani 1 1 d . . . C4 C 0.2683(5) -0.1800(3) 0.6221(3) 0.0637(7) Uani 1 1 d . . . H4 H 0.3242 -0.2584 0.5940 0.076 Uiso 1 1 calc R . . C5 C 0.3639(4) -0.0900(3) 0.6632(3) 0.0577(6) Uani 1 1 d . . . H5 H 0.4834 -0.1068 0.6612 0.069 Uiso 1 1 calc R . . C6 C 0.2795(3) 0.0264(2) 0.7077(2) 0.0463(5) Uani 1 1 d . . . C7 C 0.3740(3) 0.1208(2) 0.7569(2) 0.0452(5) Uani 1 1 d . . . C24 C 0.5163(4) 0.5052(3) 0.7298(3) 0.0626(7) Uani 1 1 d . . . H24 H 0.6132 0.5499 0.7422 0.075 Uiso 1 1 calc R . . C25 C 0.5333(5) 0.4172(3) 0.6418(3) 0.0675(7) Uani 1 1 d . . . H25 H 0.6428 0.3906 0.5867 0.081 Uiso 1 1 calc R . . C26 C 0.3608(6) 0.3758(3) 0.6495(3) 0.0774(10) Uani 1 1 d . . . H26 H 0.3324 0.3184 0.5988 0.093 Uiso 1 1 calc R . . C27 C 0.3351(5) 0.5165(3) 0.7962(3) 0.0730(8) Uani 1 1 d . . . H27 H 0.2865 0.5686 0.8618 0.088 Uiso 1 1 calc R . . C28 C 0.2361(5) 0.4345(4) 0.7461(4) 0.0855(12) Uani 1 1 d . . . H28 H 0.1092 0.4218 0.7732 0.103 Uiso 1 1 calc R . . C29 C -0.0096(6) -0.2574(4) 0.5775(3) 0.0848(10) Uani 1 1 d . . . H29A H 0.0526 -0.2630 0.4882 0.127 Uiso 1 1 calc R . . H29B H -0.1313 -0.2268 0.5882 0.127 Uiso 1 1 calc R . . H29C H -0.0164 -0.3460 0.6282 0.127 Uiso 1 1 calc R . . C32 C 0.2686(7) 0.1085(3) 1.0268(3) 0.0975(16) Uani 1 1 d . . . H32 H 0.2992 0.0179 1.0216 0.117 Uiso 1 1 calc R . . C34 C 0.1301(5) 0.2973(5) 1.0160(3) 0.0894(12) Uani 1 1 d . . . H34 H 0.0458 0.3606 1.0029 0.107 Uiso 1 1 calc R . . C35 C 0.1296(5) 0.1721(5) 0.9959(3) 0.0862(12) Uani 1 1 d . . . H35 H 0.0470 0.1320 0.9653 0.103 Uiso 1 1 calc R . . C36 C 0.2648(7) 0.3232(4) 1.0572(3) 0.0958(14) Uani 1 1 d . . . H36 H 0.2936 0.4070 1.0761 0.115 Uiso 1 1 calc R . . C37 C 0.3560(5) 0.2050(7) 1.0675(3) 0.1063(17) Uani 1 1 d . . . H37 H 0.4564 0.1923 1.0960 0.128 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 Br1 0.04265(16) 0.06602(19) 0.1044(3) -0.03113(16) -0.03533(15) 0.00874(12) Ti1 0.0355(2) 0.0361(2) 0.0451(2) -0.00851(15) -0.01530(16) 0.00258(14) O1 0.0523(10) 0.0597(10) 0.0722(11) -0.0292(9) -0.0256(9) 0.0108(8) C1 0.0544(14) 0.0542(13) 0.0514(13) -0.0152(10) -0.0190(11) 0.0035(11) C2 0.0576(15) 0.0655(16) 0.0531(13) -0.0114(12) -0.0222(12) -0.0053(12) C3 0.0769(19) 0.0548(14) 0.0455(12) -0.0075(10) -0.0235(12) -0.0141(13) C4 0.087(2) 0.0485(14) 0.0639(16) -0.0213(12) -0.0303(15) 0.0054(13) C5 0.0631(16) 0.0549(14) 0.0631(15) -0.0236(12) -0.0255(13) 0.0111(12) C6 0.0522(13) 0.0455(12) 0.0426(11) -0.0099(9) -0.0161(10) -0.0004(10) C7 0.0487(13) 0.0445(12) 0.0439(11) -0.0097(9) -0.0160(10) 0.0035(9) C24 0.0670(18) 0.0464(13) 0.0733(17) 0.0028(12) -0.0265(14) -0.0134(12) C25 0.076(2) 0.0639(17) 0.0520(14) 0.0043(12) -0.0129(13) -0.0094(14) C26 0.107(3) 0.0650(18) 0.0732(19) 0.0149(15) -0.057(2) -0.0205(18) C27 0.077(2) 0.0398(13) 0.087(2) 0.0046(13) -0.0140(16) 0.0085(13) C28 0.0558(17) 0.071(2) 0.120(3) 0.043(2) -0.0410(19) -0.0074(15) C29 0.110(3) 0.073(2) 0.084(2) -0.0196(17) -0.044(2) -0.0212(19) C32 0.136(4) 0.0466(16) 0.0626(18) 0.0083(14) 0.024(2) 0.0215(19) C34 0.066(2) 0.098(3) 0.076(2) 0.002(2) 0.0064(17) 0.030(2) C35 0.076(2) 0.123(3) 0.0490(16) -0.0013(18) -0.0103(15) -0.047(2) C36 0.150(4) 0.077(2) 0.0503(16) -0.0269(15) -0.011(2) -0.031(2) C37 0.0565(19) 0.201(5) 0.0519(17) 0.034(2) -0.0280(15) -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 Br1 Ti1 2.6911(5) . ? Ti1 C7 2.052(2) . ? Ti1 O1 2.1735(17) . ? Ti1 C36 2.322(3) . ? Ti1 C34 2.333(3) . ? Ti1 C28 2.351(3) . ? Ti1 C35 2.360(3) . ? Ti1 C26 2.360(3) . ? Ti1 C25 2.363(3) . ? Ti1 C37 2.366(3) . ? Ti1 C32 2.382(3) . ? Ti1 C27 2.389(3) . ? Ti1 C24 2.397(3) . ? O1 C7 1.225(3) . ? C1 C2 1.378(4) . ? C1 C6 1.381(4) . ? C1 H1 0.9300 . ? C2 C3 1.389(4) . ? C2 H2 0.9300 . ? C3 C4 1.365(4) . ? C3 C29 1.503(4) . ? C4 C5 1.377(4) . ? C4 H4 0.9300 . ? C5 C6 1.394(3) . ? C5 H5 0.9300 . ? C6 C7 1.457(3) . ? C24 C27 1.365(4) . ? C24 C25 1.376(4) . ? C24 H24 0.9300 . ? C25 C26 1.369(5) . ? C25 H25 0.9300 . ? C26 C28 1.384(5) . ? C26 H26 0.9300 . ? C27 C28 1.405(5) . ? C27 H27 0.9300 . ? C28 H28 0.9300 . ? C29 H29A 0.9600 . ? C29 H29B 0.9600 . ? C29 H29C 0.9600 . ? C32 C35 1.353(6) . ? C32 C37 1.381(6) . ? C32 H32 0.9300 . ? C34 C35 1.290(6) . ? C34 C36 1.307(6) . ? C34 H34 0.9300 . ? C35 H35 0.9300 . ? C36 C37 1.370(7) . ? C36 H36 0.9300 . ? C37 H37 0.9300 . ? 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 C7 Ti1 O1 33.54(8) . . ? C7 Ti1 C36 131.64(11) . . ? O1 Ti1 C36 136.00(13) . . ? C7 Ti1 C34 108.90(15) . . ? O1 Ti1 C34 132.60(13) . . ? C36 Ti1 C34 32.60(16) . . ? C7 Ti1 C28 95.65(13) . . ? O1 Ti1 C28 120.10(13) . . ? C36 Ti1 C28 98.50(18) . . ? C34 Ti1 C28 77.95(14) . . ? C7 Ti1 C35 79.20(12) . . ? O1 Ti1 C35 100.80(13) . . ? C36 Ti1 C35 54.38(13) . . ? C34 Ti1 C35 31.91(14) . . ? C28 Ti1 C35 92.06(15) . . ? C7 Ti1 C26 73.11(10) . . ? O1 Ti1 C26 88.32(11) . . ? C36 Ti1 C26 132.64(17) . . ? C34 Ti1 C26 109.30(15) . . ? C28 Ti1 C26 34.16(13) . . ? C35 Ti1 C26 111.85(13) . . ? C7 Ti1 C25 89.16(10) . . ? O1 Ti1 C25 85.79(10) . . ? C36 Ti1 C25 136.33(12) . . ? C34 Ti1 C25 132.58(12) . . ? C28 Ti1 C25 56.37(12) . . ? C35 Ti1 C25 145.28(13) . . ? C26 Ti1 C25 33.70(11) . . ? C7 Ti1 C37 109.94(18) . . ? O1 Ti1 C37 102.62(17) . . ? C36 Ti1 C37 33.96(17) . . ? C34 Ti1 C37 54.79(14) . . ? C28 Ti1 C37 131.06(17) . . ? C35 Ti1 C37 55.16(12) . . ? C26 Ti1 C37 164.09(15) . . ? C25 Ti1 C37 156.70(15) . . ? C7 Ti1 C32 78.54(12) . . ? O1 Ti1 C32 83.45(9) . . ? C36 Ti1 C32 55.67(13) . . ? C34 Ti1 C32 54.28(13) . . ? C28 Ti1 C32 125.20(16) . . ? C35 Ti1 C32 33.14(15) . . ? C26 Ti1 C32 139.53(17) . . ? C25 Ti1 C32 167.67(13) . . ? C37 Ti1 C32 33.81(16) . . ? C7 Ti1 C27 128.27(11) . . ? O1 Ti1 C27 141.29(10) . . ? C36 Ti1 C27 82.63(14) . . ? C34 Ti1 C27 79.48(13) . . ? C28 Ti1 C27 34.46(13) . . ? C35 Ti1 C27 107.02(16) . . ? C26 Ti1 C27 56.65(13) . . ? C25 Ti1 C27 56.16(11) . . ? C37 Ti1 C27 115.24(19) . . ? C32 Ti1 C27 133.32(11) . . ? C7 Ti1 C24 122.61(9) . . ? O1 Ti1 C24 115.18(9) . . ? C36 Ti1 C24 103.34(12) . . ? C34 Ti1 C24 110.90(13) . . ? C28 Ti1 C24 55.82(11) . . ? C35 Ti1 C24 140.13(15) . . ? C26 Ti1 C24 55.68(10) . . ? C25 Ti1 C24 33.60(10) . . ? C37 Ti1 C24 126.56(17) . . ? C32 Ti1 C24 158.72(12) . . ? C27 Ti1 C24 33.14(10) . . ? C7 O1 Ti1 67.80(13) . . ? C2 C1 C6 120.2(2) . . ? C2 C1 H1 119.9 . . ? C6 C1 H1 119.9 . . ? C1 C2 C3 120.7(3) . . ? C1 C2 H2 119.7 . . ? C3 C2 H2 119.7 . . ? C4 C3 C2 118.4(2) . . ? C4 C3 C29 121.5(3) . . ? C2 C3 C29 120.0(3) . . ? C3 C4 C5 122.1(3) . . ? C3 C4 H4 119.0 . . ? C5 C4 H4 119.0 . . ? C4 C5 C6 119.2(3) . . ? C4 C5 H5 120.4 . . ? C6 C5 H5 120.4 . . ? C1 C6 C5 119.3(2) . . ? C1 C6 C7 120.0(2) . . ? C5 C6 C7 120.6(2) . . ? O1 C7 C6 124.7(2) . . ? O1 C7 Ti1 78.66(14) . . ? C6 C7 Ti1 156.56(18) . . ? C27 C24 C25 109.4(3) . . ? C27 C24 Ti1 73.12(15) . . ? C25 C24 Ti1 71.86(15) . . ? C27 C24 H24 125.3 . . ? C25 C24 H24 125.3 . . ? Ti1 C24 H24 121.4 . . ? C26 C25 C24 108.0(3) . . ? C26 C25 Ti1 73.02(16) . . ? C24 C25 Ti1 74.53(15) . . ? C26 C25 H25 126.0 . . ? C24 C25 H25 126.0 . . ? Ti1 C25 H25 118.4 . . ? C25 C26 C28 108.0(3) . . ? C25 C26 Ti1 73.28(16) . . ? C28 C26 Ti1 72.55(17) . . ? C25 C26 H26 126.0 . . ? C28 C26 H26 126.0 . . ? Ti1 C26 H26 120.0 . . ? C24 C27 C28 106.7(3) . . ? C24 C27 Ti1 73.74(16) . . ? C28 C27 Ti1 71.27(16) . . ? C24 C27 H27 126.6 . . ? C28 C27 H27 126.6 . . ? Ti1 C27 H27 120.2 . . ? C26 C28 C27 107.9(3) . . ? C26 C28 Ti1 73.29(17) . . ? C27 C28 Ti1 74.26(17) . . ? C26 C28 H28 126.1 . . ? C27 C28 H28 126.1 . . ? Ti1 C28 H28 118.3 . . ? C3 C29 H29A 109.5 . . ? C3 C29 H29B 109.5 . . ? H29A C29 H29B 109.5 . . ? C3 C29 H29C 109.5 . . ? H29A C29 H29C 109.5 . . ? H29B C29 H29C 109.5 . . ? C35 C32 C37 106.3(3) . . ? C35 C32 Ti1 72.54(18) . . ? C37 C32 Ti1 72.44(19) . . ? C35 C32 H32 126.8 . . ? C37 C32 H32 126.8 . . ? Ti1 C32 H32 120.1 . . ? C35 C34 C36 110.9(4) . . ? C35 C34 Ti1 75.2(2) . . ? C36 C34 Ti1 73.2(2) . . ? C35 C34 H34 124.5 . . ? C36 C34 H34 124.5 . . ? Ti1 C34 H34 118.7 . . ? C34 C35 C32 108.9(4) . . ? C34 C35 Ti1 72.9(2) . . ? C32 C35 Ti1 74.3(2) . . ? C34 C35 H35 125.5 . . ? C32 C35 H35 125.5 . . ? Ti1 C35 H35 119.1 . . ? C34 C36 C37 107.7(4) . . ? C34 C36 Ti1 74.18(19) . . ? C37 C36 Ti1 74.8(2) . . ? C34 C36 H36 126.1 . . ? C37 C36 H36 126.1 . . ? Ti1 C36 H36 117.0 . . ? C36 C37 C32 106.0(3) . . ? C36 C37 Ti1 71.25(18) . . ? C32 C37 Ti1 73.75(18) . . ? C36 C37 H37 127.0 . . ? C32 C37 H37 127.0 . . ? Ti1 C37 H37 120.0 . . ? _diffrn_measured_fraction_theta_max 0.867 _diffrn_reflns_theta_full 28.36 _diffrn_measured_fraction_theta_full 0.867 _refine_diff_density_max 0.425 _refine_diff_density_min -0.408 _refine_diff_density_rms 0.063