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- Title
Alkenyl-Alkynylgermanes Functionalised by Lewis Acids: Intramolecular Aluminium- and Gallium-Alkyne Interactions and Potential Ge-C Bond Activation.
- Authors
Uhl, Werner; Pelties, Stefan; Rohling, Martina; Tannert, Jens
- Abstract
Treatment of various diethynylgermanes, (R1)2Ge(C≡C-R2)2 (R1 = C6H5, CH3; R1-R1 = C6H4-C6H4; R2 = CH3, CMe3, nBu, C6H5), with equimolar quantities of di( tert-butyl)aluminium or -gallium hydride, R2E-H (E = Al, Ga), afforded mixed alkenyl-alkynylgermanes, (R1)2Ge(C≡C-R2)[C{E(CMe3)2}=C(H)-R2], by reduction of one of their C≡C triple bonds. The alkenyl groups have a cis arrangement of H and Al or Ga atoms across the C=C double bonds, which reflects the kinetically favoured situation. The cis/ trans isomerisation is probably prevented from yielding thermodynamically favoured trans isomers; this is a result of an intramolecular bonding interaction between the α-carbon atoms of the remaining ethynyl groups and the coordinatively unsaturated metal atoms. The higher Lewis acidity of Al compared to Ga results in relatively short Al ···C(ethynyl) contacts (>231.2 pm) and a concomitant lengthening of the Ge-C bonds.
- Subjects
ETHYNYL compounds; ALKYNES; GERMANIUM; GALLIUM hydride; CARBON-carbon bonds; ISOMERIZATION; MOLECULAR dynamics
- Publication
European Journal of Inorganic Chemistry, 2014, Vol 2014, Issue 17, p2809
- ISSN
1434-1948
- Publication type
Article
- DOI
10.1002/ejic.201402132