Trichloro- and methyldichlorogermyl monochelates and dibromo- and dichlorogermyl bischelates derived from N,N-disubstituted amides of 2-hydroxycarboxylic acids

• Published in: Russian chemical bulletin Vol. 61; no. 3; pp. 642 - 651
• Main Authors: Airapetyan, D. V., Murasheva, T. P., Bylikin, S. Yu, Korlyukov, A. A., Shipov, A. G., Gruener, S. V., Kramarova, E. P., Negrebetskii, Vad. V., Pogozhikh, S. A., Zueva, G. Ya, Antipin, M. Yu, Baukov, Yu. I.
• Format: Journal Article
• Language: English
• Published: Boston Springer US 01.03.2012
• Subjects: Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Full Article; Inorganic Chemistry; Organic Chemistry; synthesis; X-ray diffraction study; penta- and hexacoordinate germanium compounds
• ISSN: 1066-5285; 1573-9171
• DOI: 10.1007/s11172-012-0093-7

The reactions of GeCl 4 , GeBr 4 , and MeGeCl 3 with O -trimethylsilyl derivatives of N,N -disubstituted amides of 2-hydroxycarboxylic acids afforded pentacoordinate and hexacoordinate neutral (O,O)-mono- and (O,O)-bischelates. The reactions of glycolic acid derivatives with GeX 4 produced bischelates X 2 Ge[OCH 2 C(O)NR 2 R 3 ] 2 7a,c,d (X = Cl, R 2 = R 3 = Me ( a ), (CH 2 ) 5 ( c ), (CH 2 CH 2 ) 2 O ( d )) and 8a (X = Br). By contrast, the reactions of lactic and mandelic acid derivatives with GeCl 4 and MeGeCl 3 gave monochelates Cl 3 Ge[OCH(R 1 )C(O)NR 2 R 3 ] ( S )- 9a–c (R 1 = Me) and Cl 2 MeGe[OCH(R 1 )C(O)NR 2 R 3 ] 10a (R 1 = H), ( S )- 11a,b (R 1 = Me), and ( S )- 12a (R 1 = Ph) (R 2 R 3 = (CH 2 ) 4 ( b )), respectively. According to the X-ray diffraction data, the Ge atom in bischelates 7c,d and 8a has a coordination number 6, and its coordination polyhedron can be described as a slightly distorted octahedron. In monochelates ( S )- 9a-c, 10a , ( S )- 11a,b , and ( S )- 12a , the Ge atom has a coordination number 5, and its coordination polyhedron can be described as a trigonal bipyramid with two halogen atoms or one halogen atom and one ethereal oxygen atom in equatorial positions and the halogen atom and the amide oxygen atom in the axial positions. The bonds in the axial positions are somewhat longer than the corresponding bonds in tetracoordinate Ge compounds.