Coordination Behaviour of Calcocene and its Use as a Synthon for Heteroleptic Organocalcium Compounds

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1 Supporting Information Coordination Behaviour of Calcocene and its Use as a Synthon for Heteroleptic Organocalcium Compounds Reinald Fischer, Jens Langer, Sven Krieck, Helmar Görls, Matthias Westerhausen* Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena August-Bebel-Str. 2, D Jena, Fax: , uni-jena.de Content Figure S1. Molecular structure and numbering scheme of [(py) 2 CaCp 2 ] 2 Figure S2. Molecular structure and numbering scheme of [(tmeda)cacp 2 ] 3 Table S1. Selected structural data of [(thf) 2 CaCp 2 ] (1), [(py) 2 CaCp 2 ] (2), [(tmeda)cacp 2 ] (3), [(thp) 2 CaCp 2 ] (4), and [(dme)cacp 2 ] (5) 4 Experimental Section 4 Synthesis of [(py) 2 CaCp 2 ] 4 Synthesis of [(tmeda)cacp 2 ] 4 Structure Determinations 5 Table S2. Crystal data and refinement details for the X-ray crystal structure determinations of the calcocenes of the type [(L)CaCp 2 ] 6 References 6 1

2 Figure S1: Molecular structure and numbering scheme of [(py) 2 CaCp 2 ] (2). The ellipsoids represent a probability of 40%, H atoms are neglected for clarity reasons. 2

3 Figure 2: Molecular structure and numbering scheme of [(tmeda)cacp 2 ] (3). The ellipsoids represent a probability of 40%, hydrogen atoms are omitted for clarity reasons. 3

4 Table S1: Selected structural data of [(thf) 2 CaCp 2 ] (1), S1 [(py) 2 CaCp 2 ] (2), [(tmeda)cacp 2 ] (3), [(thp) 2 CaCp 2 ] (4), and [(dme)cacp 2 ] (5) S1 (bond lengths [Å] and angles [ ]). Ca-Cp cent Cp cent -Ca-Cp cent Ca-L L-Ca-L [(thf) 2 CaCp 2 ] (1) 2.419(3) 129.0(1) 2.396(2) 81.4(1) [(py) 2 CaCp 2 ] (2) 2.430(2), 128.5(1) 2.522(2), 84.96(5) 2.440(2) 2.550(2) [(tmeda)cacp 2 ] (3) 2.436(3) 127.1(1) 2.627(2) 71.9(1) [(thp) 2 CaCp 2 ] (4) 2.433(2) 134.9(1) 2.381(1) 88.31(6) [(dme)cacp 2 ] (5) 2.408(4) 132.8(1) 2.418(2) 68.3(1) Experimental Section General: All manipulations were carried out in an argon atmosphere under anaerobic conditions. Prior to use, all solvents were thoroughly dried and distilled in an argon atmosphere. The reported calcocene compounds are moisture and air sensitive. 1 H NMR and 13 C NMR spectra were recorded at [D 8 ]THF or [D 6 ]benzene solutions at ambient temperature on a Bruker AC 200 MHz or a Bruker AC 400 MHz spectrometer. All spectra were referenced to deuterated THF or benzene as an internal standard. DEI-mass spectra were obtained on a Finnigan MAT SSQ 710 system (2,4-dimethoxy-benzylalcohol as matrix), IR measurements were carried out on a Perkin Elmer System 2000 FT-IR. Decomposition points were measured with a Reichert-Jung Apparatus Type Complexes 2 and 3 were reported earlier, S2 however, their synthesis starting from [(thf) 2 CaCp 2 ] (1) is described. Synthesis of [(py) 2 CaCp 2 ] (2): Complex [(thf) 2 CaCp 2 ] (1) (1.60 g, 5.09 mmol) were dissolved at 20 C in 25 ml of pyridine. The volume was reduced to 20 ml and stored at - 20 C. The precipitated colorless crystals were collected and dried in vacuo. Yield: 1.14 g (68.2%). 1 H NMR ([D 6 ]benzene/pyridine): δ 6.07 (Cp). 13 C{ 1 H} NMR ([D 6 ]benzene/pyridine): δ (Cp). Synthesis of [(tmeda)cacp 2 ] (3): Solid [(thf) 2 CaCp 2 ] (1) (0.60 g, 1.91 mmol) was suspended in diethyl ether (25 ml) and tmeda (2 ml) was added dropwise resulting in a clear solution. Reduction of the volume to 10 ml and storage at +4 C led to precipitation of large colorless prisms. The collected crystals were washed with cold n-pentane (5 ml) and gently dried in 4

5 vacuum yielding 0.52 g (1.82 mmol, 95 %) of [(tmeda)cacp 2 ] (3). Physical Data: Decomposition above 76 C. Anal. Calc. for C 16 H 26 CaN 2 ( g mol -1 ): Ca 13.99; found: Ca H NMR (25 C, [D 6 ]benzene): δ 1.85 (12H, s, CH 3, tmeda), 1.88 (4H, s, CH 2, tmeda), 6.04 (10H, s, Cp). 13 C{ 1 H} NMR (25 C, [D 6 ]benzene): δ 46.1 (4C, CH 3, tmeda), 57.5 (2C, CH 2, tmeda), (10C, br, Cp). MS (EI, m/z, [%]): 116 (tmeda) [15], 66 (CpH) [83], 58 (tmeda/2) [100]. IR (Nujol, KBr, cm -1 ) ν: 2931 vs(br), 1718 w, 1701 w, 1610 w, 1578 w, 1460 vs, 1377 vs, 1289 s, 1260 m, 1245 m, 1165 m, 1125 m, 1097 m, 1075 m, 1030 m, 1006 s, 948 m, 891 m, 791 m, 755 s, 722 s, 644s. Structure Determinations. The intensity data for the compounds were collected on a Nonius KappaCCD diffractometer using graphite-monochromated Mo-K α radiation. Data were corrected for Lorentz and polarization effects but not for absorption effects. S3,S4 The structures were solved by direct methods (SHELXS S5 ) and refined by full-matrix least squares techniques against F 2 o (SHELXL-97 S5 ). All hydrogen atoms were included at calculated positions with fixed thermal parameters. All non-hydrogen atoms were refined anisotropically. S5 Crystallographic data as well as structure solution and refinement details are summarized in Table S2. XP (SIEMENS Analytical X-ray Instruments, Inc.) was used for structure representations. 5

6 Table S2: Crystal data and refinement details for the X-ray crystal structure determinations of the calcocenes of the type [(L)CaCp 2 ] Compound 2 3 formula C 20 H 20 CaN 2 C 16 H 26 CaN 2 fw (g mol -1 ) T/ C -90(2) -90(2) crystal system monoclinic monoclinic space group P 2 1 /n C 2/c a/ Å (5) (9) b/ Å (5) (5) c/ Å (7) (9) α/ β/ (3) (2) γ/ V/Å (14) (17) Z 4 4 ρ (g cm -3 ) µ (mm -1 ) measured data data with I > 2σ(I) unique data (R int ) 4101/ / wr 2 (all data, on F 2 ) a) R 1 (I > 2σ(I)) a) S b) Res. dens./e Å / / absorpt method NONE NONE CCDC No a) Definition of the R indices: R 1 = (Σ F o - F c )/Σ F o ; wr 2 = {Σ[w(F 2 o -F 2 c ) 2 ]/Σ[w(F 2 o ) 2 ]} 1/2 with w -1 = σ 2 (F 2 o ) + (ap) 2 +bp; P = [2F 2 c + Max(F 2 O ]/3; b) s = {Σ[w(F 2 o -F 2 c ) 2 ]/(N o -N p )} 1/2. References [S1] Gärtner, M.; Görls, H.; Westerhausen, M. Organometallics 2007, 26, [S2] Allan, K. A.; Gowenlock, B. G.; Lindsell, W. E. J. Organomet. Chem. 1973, 55, [S3] COLLECT, Data Collection Software; Nonius B.V., Netherlands, [S4] Otwinowski, Z.; Minor, W. in Carter, C. W.; Sweet, R. M. (eds.): Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A: Processing of X-Ray Diffraction Data Collected in Oscillation Mode, pp , Academic Press [S5] Sheldrick, G. M. Acta Cryst A64,