Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2001 data_global #=========================================================================== # 0. AUDIT DETAILS _audit_creation_date 8-Apr-00 _audit_creation_method 'PLATON option' _audit_update_record ; 8-Apr-00 Updated by the Author E.H. 10-Apr-00 Updated by the Author E.H. 12-Oct-00 Updated by the Author E.H. 6-Dec-00 Updated by the Author E.H. ; #=========================================================================== # 1. SUBMISSION DETAILS #=========================================================================== # Name and address of author for X-ray correspondence _publ_contact_author ; Dr Fritz E Kuhn Anorganisch-Chemisches Institut Technishe Universitat Munchen Litchtenbergstr 4 Muchen D-85747 Garching bei M\"unchen GERMANY ; _publ_requested_journal 'J.C.S., Dalton Trans.' _publ_requested_coeditor_name ? _publ_contact_letter # Include date of submission ; Date of submission: 10-Nov-00 ; #=========================================================================== # 2. PROCESSING SUMMARY (JOURNAL OFFICE ONLY) #=========================================================================== _journal_date_recd_electronic ? _journal_date_to_coeditor ? _journal_date_from_coeditor ? _journal_date_accepted ? _journal_date_printers_first ? _journal_date_printers_final ? _journal_date_proofs_out ? _journal_date_proofs_in ? _journal_coeditor_name ? _journal_coeditor_code ? _journal_coeditor_notes ; ? ; _journal_techeditor_code ? _journal_techeditor_notes ; ? ; _journal_coden_Cambridge 186 _journal_name_full ? _journal_year ? _journal_volume ? _journal_issue ? _journal_page_first ? _journal_page_last ? _journal_suppl_publ_number ? _journal_suppl_publ_pages ? #=========================================================================== # 3. TITLE AND AUTHOR LIST #=========================================================================== _publ_section_title ; Molybdenum(VI) cis-Dioxo Complexes Bearing (poly)-Pyrazolyl Methane and (poly)-Pyrazolyl Borate Ligands: Syntheses, Characterization and Catalytic Applications ; # The loop structure below should contain the names and adresses of all # authors, in the required order of publication. Repeat as necessary. loop_ _publ_author_name _publ_author_address 'Santos, A. M.' ; Anorganisch-chemisches Institut der Technischen Universit\"at M\"unchen Lichtenbergstrasse 4 D-85747 Garching bei M\"unchen ; 'K\"uhn, F. E.' ; Anorganisch-chemisches Institut der Technischen Universit\"at M\"unchen Lichtenbergstrasse 4 D-85747 Garching bei M\"unchen ; 'Lucas, I.' ; Instituto de Tecnologia Quimica e Biologica da Universidade Nova de Lisboa, Quinta do Marques, EAN, Apt 127, 2781-901 Oeiras Portugal ; 'Rom\"ao, C. C.' ; Instituto de Tecnologia Quimica e Biologica da Universidade Nova de Lisboa, Quinta do Marques, EAN, Apt 127, 2781-901 Oeiras Portugal ; 'Herdtweck, E.' ; Anorganisch-chemisches Institut der Technischen Universit\"at M\"unchen Lichtenbergstrasse 4 D-85747 Garching bei M\"unchen ; #=========================================================================== # 4. TEXT #=========================================================================== _publ_section_abstract ; Reaction of MoOCl2(THF)2 with mono- and bidentate nitrogen donor ligands of the pyrazole type leads to octahedral complexes of the formula MoO2Cl2L2. One of these compounds has been examined by X-ray crystallography. Reaction of MoO2X2(THF)2 (X == Cl, Br) with tridentate ligands, e. g. trispyrazolylmethane or trispyrazolyborate leads to the replacement of both coordinated solvent molecules and one of the chlorine ligands. Depending on the donor ability and the steric bulk of the ligand rapid ligand rotation is observed at room temperature in some cases. At lower temperatures the structures are more rigid. 95Mo-NMR spectroscopy proves to be a straightforward mean to distinguish between the different ligand environment of the Mo(VI) centre. The turnover frequencies of the described complexes in olefin epoxidation with t-butyl hydroperoxide as oxidizing agent are in the range of 200 - 400 1/h. This relatively low activity is compensated by the ease of handling and the stability of the complexes. ; # Insert blank lines between paragraphs _publ_section_comment ; none ; _publ_section_experimental ; none ; # Insert blank lines between references _publ_section_references ; Allen, F.H., Kennard, O. & Taylor, R. (1983). Acc. Chem. Res. 16, 146-153. Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993) J. Appl. Cryst. 26, 343-350. Sheldrick, G.M. SHELXL97. Program for crystal structure refinement. University of G\"ottingen, Germany, 1997. Spek, A.L. (1997). HELENA, Program for Datareduction, Utrecht University, The Netherlands. Wilson, A.J.C. (1992) Ed. International Tables for Crystallography, Volume C, Kluwer Academic Publishers, Dordrecht, The Netherlands. ; _publ_section_figure_captions ; none ; _publ_section_acknowledgements ; none ; _publ_section_table_legends ; none ; #=========================================================================== data_ANAE-4073-173 _database_code_CSD 154166 #=========================================================================== # 5. CHEMICAL DATA #=========================================================================== _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety 'C9 H12 Cl2 Mo N4 O2' _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C9 H12 Cl2 Mo N4 O2' _chemical_formula_weight 375.07 _chemical_compound_source 'see text' loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mo Mo -1.6832 0.6857 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 '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' C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' #=========================================================================== # 6. CRYSTAL DATA #=========================================================================== _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_Hall '-P 2ac 2ab' _symmetry_space_group_name_H-M 'P b c a' loop_ _symmetry_equiv_pos_as_xyz x,y,z 1/2-x,-y,1/2+z 1/2+x,1/2-y,-z -x,1/2+y,1/2-z -x,-y,-z 1/2+x,y,1/2-z 1/2-x,1/2+y,z x,1/2-y,1/2+z _cell_length_a 12.0163(2) _cell_length_b 15.8867(4) _cell_length_c 14.4079(3) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 2750.5(1) _cell_formula_units_Z 8 _cell_measurement_temperature 173(1) _cell_measurement_reflns_used 42799 _cell_measurement_theta_min 1.00 _cell_measurement_theta_max 25.35 _exptl_crystal_description 'prism' _exptl_crystal_colour 'colorless' _exptl_crystal_size_max 0.38 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.23 _exptl_crystal_density_meas none _exptl_crystal_density_diffrn 1.812 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1488 _exptl_absorpt_coefficient_mu 1.341 _exptl_absorpt_correction_type 'empirical' _exptl_absorpt_correction_T_min 0.625 _exptl_absorpt_correction_T_max 0.735 _exptl_special_details ; Diffractometer operator E. Herdtweck scanspeed 2x10 s per film repetition 1 425 films measured in 6 data sets with delta_phi=1 and with delta_omega=1 ; _exptl_absorpt_process_details ; Denzo-SNM; Scale-Pack ; _publ_section_exptl_prep ; The crystal was fixed in a capillary with perfluorinated ether and transfered to the diffractometer. ; _publ_section_exptl_refinement ; Straight forward. Hydrogen atoms could be located in the difference Fourier maps and refined freely. ; #=========================================================================== # 7. EXPERIMENTAL DATA #=========================================================================== _diffrn_ambient_temperature 173(1) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_source 'NONIUS FR 591 rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'four-circle diffractometer' _diffrn_measurement_device_type 'Kappa CCD (Nonius)' _diffrn_measurement_method ' phi- and omega-rotation ' _diffrn_detector 'CCD plate' _diffrn_detector_area_resol_mean 18 # 9 for binned mode _diffrn_standards_number none _diffrn_standards_interval_count none _diffrn_standards_interval_time none _diffrn_standards_decay_% 0 # number of measured reflections (redundant set) _diffrn_reflns_number 24230 _diffrn_reflns_av_R_equivalents 0.039 _diffrn_reflns_av_sigmaI/netI 0.0195 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -19 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 2.55 _diffrn_reflns_theta_max 25.40 _reflns_number_total 2519 _reflns_number_gt 2275 _reflns_threshold_expression >2sigma(I) _diffrn_reflns_reduction_process ; with the Kappa CCD software Scale-Pack ; _computing_data_collection 'Kappa CCD (Nonius)' _computing_cell_refinement 'Denzo and HKL' _computing_data_reduction 'Denzo and HKL' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1987)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'PLATON (Spek, 1999)' _computing_publication_material 'PLATON (Spek, 1999)' #=========================================================================== # 8. REFINEMENT DATA #=========================================================================== _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating R_factor_obs 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 sigma _refine_ls_weighting_details 'w=1/[\s^2^(Fo^2^)+(0.0245P)^2^+2.8893P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2519 _refine_ls_number_parameters 211 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0277 _refine_ls_R_factor_gt 0.0243 _refine_ls_wR_factor_ref 0.0602 _refine_ls_wR_factor_gt 0.0585 _refine_ls_goodness_of_fit_ref 1.108 _refine_ls_restrained_S_all 1.108 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 25.40 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.466 _refine_diff_density_min -0.521 _refine_diff_density_rms 0.065 #=========================================================================== # 9. ATOMIC COORDINATES AND THERMAL PARAMETERS #=========================================================================== loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv Mo Mo Uani 0.19840(2) -0.38007(1) 0.35760(1) 1.000 0.0221(1) Cl1 Cl Uani 0.20586(6) -0.23189(4) 0.35236(5) 1.000 0.0364(2) Cl2 Cl Uani 0.22284(5) -0.52366(3) 0.40211(4) 1.000 0.0298(2) O1 O Uani 0.25308(16) -0.39546(11) 0.25065(12) 1.000 0.0356(6) O2 O Uani 0.05917(15) -0.38619(11) 0.34269(12) 1.000 0.0334(6) N11 N Uani 0.41382(15) -0.37239(12) 0.50679(14) 1.000 0.0254(6) N12 N Uani 0.37488(15) -0.36786(12) 0.41817(13) 1.000 0.0245(6) N21 N Uani 0.23917(15) -0.38306(11) 0.58616(13) 1.000 0.0210(6) N22 N Uani 0.16443(15) -0.36967(11) 0.51603(13) 1.000 0.0214(6) C1 C Uani 0.34824(18) -0.34080(15) 0.58669(16) 1.000 0.0254(7) C2 C Uani 0.4091(2) -0.3634(2) 0.6758(2) 1.000 0.0392(10) C3 C Uani 0.3321(2) -0.24645(17) 0.5787(2) 1.000 0.0353(8) C13 C Uani 0.4627(2) -0.38369(17) 0.36362(19) 1.000 0.0347(9) C14 C Uani 0.5573(2) -0.3977(2) 0.4159(2) 1.000 0.0428(10) C15 C Uani 0.5240(2) -0.38932(19) 0.5061(2) 1.000 0.0413(9) C23 C Uani 0.0686(2) -0.40203(15) 0.54717(18) 1.000 0.0274(7) C24 C Uani 0.0806(2) -0.43458(17) 0.63480(18) 1.000 0.0331(8) C25 C Uani 0.1885(2) -0.42161(16) 0.65845(18) 1.000 0.0293(8) H21 H Uiso 0.423(2) -0.423(2) 0.679(2) 1.000 0.042(8) H22 H Uiso 0.367(2) -0.3430(18) 0.726(2) 1.000 0.044(8) H23 H Uiso 0.474(3) -0.3364(18) 0.677(2) 1.000 0.041(8) H31 H Uiso 0.405(3) -0.2202(19) 0.580(2) 1.000 0.050(9) H32 H Uiso 0.290(2) -0.2269(18) 0.631(2) 1.000 0.038(8) H33 H Uiso 0.297(2) -0.2308(18) 0.524(2) 1.000 0.036(8) H131 H Uiso 0.455(2) -0.3863(16) 0.302(2) 1.000 0.037(8) H141 H Uiso 0.628(3) -0.410(2) 0.398(2) 1.000 0.055(9) H151 H Uiso 0.565(3) -0.3930(18) 0.559(2) 1.000 0.048(9) H231 H Uiso 0.009(2) -0.4005(14) 0.5085(18) 1.000 0.022(6) H241 H Uiso 0.031(2) -0.4589(18) 0.667(2) 1.000 0.043(8) H251 H Uiso 0.228(2) -0.4330(17) 0.712(2) 1.000 0.036(7) 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 Mo 0.0282(1) 0.0218(1) 0.0164(1) 0.0005(1) -0.0026(1) 0.0015(1) Cl1 0.0516(4) 0.0208(3) 0.0367(4) 0.0056(2) 0.0044(3) 0.0032(2) Cl2 0.0371(3) 0.0204(3) 0.0320(3) -0.0003(2) -0.0030(2) 0.0026(2) O1 0.0498(11) 0.0366(9) 0.0205(9) -0.0006(8) 0.0017(8) 0.0058(8) O2 0.0327(10) 0.0371(10) 0.0305(10) 0.0040(7) -0.0113(8) 0.0010(7) N11 0.0191(9) 0.0362(11) 0.0209(10) -0.0068(8) 0.0020(8) -0.0023(8) N12 0.0238(10) 0.0326(10) 0.0172(10) -0.0028(8) 0.0021(8) -0.0026(8) N21 0.0213(9) 0.0263(10) 0.0153(10) -0.0011(7) 0.0013(7) -0.0013(8) N22 0.0197(9) 0.0267(10) 0.0177(10) -0.0001(8) -0.0011(7) -0.0002(8) C1 0.0199(11) 0.0349(13) 0.0213(12) -0.0079(10) 0.0016(9) -0.0046(10) C2 0.0277(14) 0.063(2) 0.0270(15) -0.0080(14) -0.0043(12) -0.0028(14) C3 0.0386(14) 0.0332(14) 0.0342(15) -0.0124(12) 0.0060(13) -0.0107(12) C13 0.0366(15) 0.0400(15) 0.0274(15) -0.0073(12) 0.0137(11) -0.0062(11) C14 0.0204(13) 0.0611(18) 0.0468(18) -0.0176(14) 0.0095(12) -0.0041(12) C15 0.0223(13) 0.0598(18) 0.0419(17) -0.0136(14) -0.0016(12) 0.0010(12) C23 0.0207(11) 0.0328(13) 0.0287(13) -0.0035(10) 0.0021(10) -0.0012(10) C24 0.0334(14) 0.0377(14) 0.0281(14) 0.0008(11) 0.0092(11) -0.0108(12) C25 0.0369(14) 0.0313(13) 0.0196(13) 0.0026(10) 0.0009(10) -0.0030(10) #=========================================================================== # 10. MOLECULAR GEOMETRY #=========================================================================== _geom_special_details ; Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All esds are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag Mo Cl1 2.3570(7) . . yes Mo Cl2 2.3877(5) . . yes Mo O1 1.6929(18) . . yes Mo O2 1.6896(18) . . yes Mo N12 2.3014(18) . . yes Mo N22 2.3247(19) . . yes N11 N12 1.362(3) . . yes N11 C1 1.483(3) . . yes N11 C15 1.351(3) . . yes N12 C13 1.340(3) . . yes N21 N22 1.368(3) . . yes N21 C1 1.473(3) . . yes N21 C25 1.353(3) . . yes N22 C23 1.339(3) . . yes C1 C2 1.521(4) . . no C1 C3 1.516(4) . . no C13 C14 1.382(4) . . no C14 C15 1.366(4) . . no C23 C24 1.372(4) . . no C24 C25 1.356(3) . . no C2 H21 0.96(3) . . no C2 H22 0.94(3) . . no C2 H23 0.89(3) . . no C3 H31 0.97(4) . . no C3 H32 0.96(3) . . no C3 H33 0.93(3) . . no C13 H131 0.89(3) . . no C14 H141 0.91(4) . . no C15 H151 0.91(3) . . no C23 H231 0.91(2) . . no C24 H241 0.85(3) . . no C25 H251 0.92(3) . . no 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag Cl1 Mo Cl2 163.36(2) . . . yes Cl1 Mo O1 95.76(6) . . . yes Cl1 Mo O2 95.22(6) . . . yes Cl1 Mo N12 83.85(5) . . . yes Cl1 Mo N22 88.12(5) . . . yes Cl2 Mo O1 93.37(6) . . . yes Cl2 Mo O2 95.80(6) . . . yes Cl2 Mo N12 82.26(5) . . . yes Cl2 Mo N22 79.97(5) . . . yes O1 Mo O2 105.09(9) . . . yes O1 Mo N12 89.98(8) . . . yes O1 Mo N22 166.45(8) . . . yes O2 Mo N12 164.91(8) . . . yes O2 Mo N22 87.42(7) . . . yes N12 Mo N22 77.50(6) . . . yes N12 N11 C1 121.84(17) . . . yes N12 N11 C15 109.9(2) . . . yes C1 N11 C15 126.4(2) . . . yes Mo N12 N11 131.89(14) . . . yes Mo N12 C13 119.18(16) . . . yes N11 N12 C13 105.63(18) . . . yes N22 N21 C1 121.13(17) . . . yes N22 N21 C25 110.09(18) . . . yes C1 N21 C25 127.08(19) . . . yes Mo N22 N21 126.78(13) . . . yes Mo N22 C23 116.93(15) . . . yes N21 N22 C23 104.92(18) . . . yes N11 C1 N21 108.34(18) . . . yes N11 C1 C2 108.67(19) . . . yes N11 C1 C3 110.11(19) . . . yes N21 C1 C2 108.95(19) . . . yes N21 C1 C3 109.67(18) . . . yes C2 C1 C3 111.0(2) . . . no N12 C13 C14 111.0(2) . . . yes C13 C14 C15 105.2(2) . . . no N11 C15 C14 108.3(2) . . . yes N22 C23 C24 111.3(2) . . . yes C23 C24 C25 105.9(2) . . . no N21 C25 C24 107.8(2) . . . yes C1 C2 H21 110.9(17) . . . no C1 C2 H22 108.0(16) . . . no C1 C2 H23 108.9(19) . . . no H21 C2 H22 113(2) . . . no H21 C2 H23 109(2) . . . no H22 C2 H23 107(2) . . . no C1 C3 H31 107.9(19) . . . no C1 C3 H32 109.1(17) . . . no C1 C3 H33 112.8(18) . . . no H31 C3 H32 109(2) . . . no H31 C3 H33 108(2) . . . no H32 C3 H33 110(2) . . . no N12 C13 H131 120.7(16) . . . no C14 C13 H131 128.3(16) . . . no C13 C14 H141 130.5(19) . . . no C15 C14 H141 124.4(19) . . . no N11 C15 H151 123(2) . . . no C14 C15 H151 129(2) . . . no N22 C23 H231 117.6(16) . . . no C24 C23 H231 131.1(16) . . . no C23 C24 H241 126.9(18) . . . no C25 C24 H241 127.1(18) . . . no N21 C25 H251 120.0(16) . . . no C24 C25 H251 132.2(16) . . . no # End of Crystallographic Information File --CCDCCONTENTSEPARATOR--