2 D. A. Armitage, in The chemistry of organic silicon compounds, ed.
S. Patai and Z. Rappoport, John Wiley & Sons Ltd., London,
1989, pp. 1401–1409.
3 (a) D. Kobelt, E. F. Paulus and H. Scherer, Acta Crystallogr., Sect.
B, 1972, 28, 2323; (b) A. G. Davies, L. Smith and P. J.
Smith, J. Organomet. Chem., 1972, 39, 279; (c) H. Berwe and
A. Haas, Chem. Ber., 1987, 120, 1175; (d) W. Ando, T. Kadowaki,
Y. Kabe and M. Ishii, Angew. Chem., Int. Ed. Engl., 1992, 31, 59;
(e) M. Weidenbruch, J. Schlaefke, A. Schafer, K. Peters, H. G. von
¨
Schnering and H. Marsmann, Angew. Chem., Int. Ed. Engl., 1994,
33, 1846; (f) W. Ando, T. Kadowaki, A. Watanabe, M. Choi,
Y. Kabe, T. Erata and M. Ishii, Nippon Kagaku Kaishi, 1994, 3,
214; (g) K. Wraage, T. Pape, R. Herbst-Irmer, M. Noltemeyer,
H.-G. Schmidt and H. W. Roesky, Eur. J. Inorg. Chem., 1999, 869;
(h) C. Wagner, C. Raschke and K. Merzweiler, Appl. Organomet.
Chem., 2004, 18, 147.
Fig. 2 Molecular structures of 2 (left hand side) and 3 (right hand
side); disorder and H atoms omitted for clarity. Selected distances [A]: 2:
Ge–Te 2.555(2)–2.575(2), Ge–Ge 2.451(2), Ge–C 1.979(12)–1.991(11);
3: Ge–Te 2.560(3)–2.593(3), Ge–Ge 2.482(4), Ge–C 1.972(18)–2.01(2).
4 (a) K. Moedritzer, Inorg. Chem., 1967, 6, 1248; (b) R. H.
Benno and C. J. Fritchie, Jr., J. Chem. Soc., Dalton Trans., 1973,
543; (c) A. Haas, H.-J. Kutsch and C. Kruger, Chem. Ber.,
¨
1987, 120, 1045; (d) B. Krebs, Angew. Chem., Int. Ed. Engl.,
1983, 22, 113; (e) M. N. Bochkarev, L. P. Maiorova,
N. S. Vyazankin and G. A. Razuvaev, J. Organomet. Chem.,
1974, 82, 65; (f) S. Pohl, Angew. Chem., Int. Ed. Engl., 1976, 15,
162; (g) S. Pohl, U. Seyer and B. Krebs, Z. Naturforsch., B, 1981,
36, 1432.
5 (a) M. Unno, Y. Kawai, H. Shioyama and H. Matsumoto, Organo-
metallics, 1997, 16, 4428; (b) B. Celaries, G. Rima, L. Court,
´
Scheme 2 Synthesis of Si/Se noradamantane-type complexes.20
C. Lion and J.-D. Laval, Met.-Based Drugs, 2001, 8, 199.
6 R. Hauser and K. Merzweiler, Z. Anorg. Allg. Chem., 2002, 628,
905.
7 Z. Hassanzadeh Fard, L. Xiong, C. Muller, M. Ho"ynska and
¨
S. Dehnen, Chem.–Eur. J., 2009, 15, 6595.
8 Z. Hassanzadeh Fard, C. Muller, T. Harmening, R. Pottgen and
¨
¨
S. Dehnen, Angew. Chem., Int. Ed., 2009, 48, 4441.
9 Z. Hassanzadeh Fard, M. R. Halvagar and S. Dehnen, J. Am.
Chem. Soc., 2010, 32, 2848.
10 (a) T. Matsumoto, Y. Nakaya and K. Tatsumi, Organometallics,
2006, 25, 4835; (b) T. Matsumoto, Y. Matsui, M. Ito and
K. Tatsumi, Inorg. Chem., 2008, 47, 1901; (c) T. Matsumoto,
Y. Matsui, M. Ito and K. Tatsumi, Chem.–Asian J., 2008,
3, 607.
Fig. 3 Molecular structure of the anion in 4. The [N2H5]+ cation is
not shown. Selected distances [A]: Ge–Te 2.468(2)–2.513(2), Ge–C
1.998(13)–2.021(13), Ge–N 2.027(12)–2.038(12).
11 M. R. Halvagar, Z. Hassanzadeh Fard, L. Xiong and S. Dehnen,
Inorg. Chem., 2009, 48, 7373.
12 C. Pohlker, I. Schellenberg, R. Pottgen and S. Dehnen, Chem.
¨
Commun., 2010, 46, 2605.
13 D. Dakternieks, K. Jurkschat, H. Wu and E. R. T. Tiekink,
Organometallics, 1993, 12, 2788.
14 G. Ramaker, W. Saak, D. Haase and M. Weidenbruch, Organo-
metallics, 2003, 22, 5212.
15 (a) R. Caliandro, B. Carrozzini, G. L. Cascarano, L. De Caro,
C. Giacovazzo, A. Mazzone and D. Siliqi, J. Appl. Crystallogr.,
2008, 41, 548; (b) A. Perrakis, R. Morris and V. S. Lamzin, Nat.
Struct. Biol., 1999, 6, 5.
¨
another reaction took place here, that ended up with the formation
of the hydrazonium salt 4 of the functionalized monomeric
anion [R4GeTe2]ꢀ (Fig. 3); in the latter, the organic substituent
also establishes a five-membered ring including a Ge–N bond
(2.027(12)–2.038(12) A).
The observed results illustrate that—in contrast to the
known (RGe)/S system—an O - Ge or N - Ge interaction
is possible in (RGe)/Te complexes, owing to longer Ge–E
bonds and thus lower steric repulsion; as a consequence,
unexpected products adopting a DD-type Ge/E skeleton or
representing a monomeric unit are observed that feature
these intramolecular donor–acceptor bonds. Moreover, for
COOH-terminated ligands, uncommon NA-type Ge/Te complexes
bearing a Ge–Ge bond are preferred for this particular (RT)/E
combination, as confirmed by DFT calculations.
16 M. Kuchta and G. Parkin, J. Chem. Soc., Chem. Commun., 1994, 1351.
17 W. Koch and M. C. Holthausen, A Chemist’s Guide to Density
Functional Theory, Wiley-VCH, 2001.
18 TURBOMOLE V5.10, Turbomole GmbH, Karlsruhe, 2008.
19 J. Weidlein, U. Muller and K. Dehnicke, Schwingungsspektroskopie,
¨
Georg Thieme Verlag, Stuttgart, 2nd edn, 1988, p. 46.
20 U. Herzog and G. Rheinwald, J. Organomet. Chem., 2001, 628, 133.
21 C. Eabom and K. C. Pandle, J. Chem. Soc., 1960, 3200.
22 I. S. Tulokhonova and M. G. Voronkov, Inorg. Chem. Commun.,
1998, 10, 379.
23 M. Tanaka, T. Hoomashi, T. Hayashi and T. Sakakura, Appl.
Organomet. Chem., 1988, 4, 291.
24 (a) V. V. Jouikov, Usp. Khim., 1997, 66, 564; (b) M. Tanabe,
N. Ishikawa, M. Hanzawa and K. Osakada, Organometallics,
2008, 27, 5152.
We thank the German Science Foundation (DFG) for
financial support and Dr K. Harms for valuable help with
the twinned X-ray structure analyses.
¨
25 B. Eisenmann, H. Schafer and H. Schwerer, Z. Naturforsch., B,
1983, 38, 924.
Notes and references
1 (a) P. Pfeiffer and R. Lehnardt, Chem. Ber., 1903, 36, 3027;
(b) C. Dorfelt, A. Janeck, D. Kobelt, E. F. Paulus and
H. Scherer, J. Organomet. Chem., 1968, 14, P22.
26 A. Sekiguchi, T. Yatabe, H. Kamatani, C. Kabuto and H. Sakurai,
J. Am. Chem. Soc., 1992, 15, 6260.
27 S. G. Bratsch, J. Phys. Chem. Ref. Data, 1989, 18, 1.
c
This journal is The Royal Society of Chemistry 2011
Chem. Commun., 2011, 47, 1881–1883 1883