Reaction of the chlorogermylene ArGeCl [Ar ) 2,6-bis((diethylamino)methyl)phenyl] with lithium amides afforded the aminogermylenes ArGeNR 2 1 (1a, R ) SiMe 3 ; 1b, R ) i Pr); 1a was structurally analyzed by X-ray diffraction. A protic reagent such as 2,4,6-trimethylphenol (Ar′OH) reacts with 1b, leading to the mesityloxygermylene ArGeOAr′ 2. Subsequent hydrolysis of tungsten complexes 1‚W(CO) 5 gave ArGeOH‚W(CO) 5 , 3. From 1a, ArGeOSiMe 3 ‚ W(CO) 5 (4) also was obtained. Compounds 3 and 4 are the first stable hydroxy-and siloxygermylene complexes. X-ray analysis of 3 shows an increased coordination of the sidechain nitrogen atoms to the germanium resulting from the complexation GefW. This complexation can also explain the significant acidity of the hydroxy group in 3, in the same range as triphenylgermanol Ph 3 GeOH.
Not only steric shielding but also resonance with a delocalized π‐electron system can help to stabilize nonclassical multiple bonds. Thus, despite high steric demands, 15 C atoms and the Ge atom of the title compound 1 lie nearly in the same plane. The experimental finding is in agreement with the result of a MNDO calculation.
There is now a great deal of interest in group 13, 14, and 15 elements in low coordination states.1 Since 1981, several new compounds of the type M=M/ (M and M': group 13, 14, and 15 elements) withbonds have been reported. In organogermanium chemistry, the first stable derivatives with a sp2-hybridized germanium have only been prepared very recently: they are the digermenes R2Ge=GeR22 (R = bis(trimethylsilvl) methyl,23 2,6-dimethylphenyl,2b 2,6-diethylphenyl2c), the germaphosphene R2Ge=PR,3a (R = mesityl, R' = 2,4,6-tri-rert-butylphenyl), and the germaimines R2Ge=NR,3b (R = (Me3Si)2N, R' = N=C-(R,,)(R,,/))• Germenes R2Ge=CR2' have long been speculated as reactive intermediates and could only be characterized by trapping reactions.lc,d'4'5
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