Journal of Organometallic Chemistry p. 321 - 332 (1997)
Update date:2022-07-26
Topics:
Fischer, Helmut
Podschadly, Oliver
Roth, Gerhard
Herminghaus, Stefan
Klewitz, Steffen
Heck, Juergen
Houbrechts, Stephan
Meyer, Timo
The pentacarbonyl(vinylidene)chromium complexes [(CO)5Cr=C=C(R)R′] (1) [C(R)R′ = CPh2 (a), C(CH2)5 (b), CMe2, (c), C(Me)H (d)] react with 1-diethylamino-1-propyne, MeC≡CNEt2, by regiospecific addition of the C≡C bond of the alkyne to the C≡C bond of the vinylidene ligand to form the cyclobutenylidene complexes [(CO)5Cr=C=C(Me)=C(NEt2)=C(R)R′] (2a-d). The analogous reaction of [(CO)5Cr=C=C(Ph)H] with MeC≡CNEt2 affords via cycloaddition and formal [1,3]-H shift the complex [(CQ)5Cr=C=C(Ph)=C(NEt2)=C(Me)H] (3). The cycloadditions of Me2NC≡CNMe2 and MeC≡COEt to 1b give [(CO)5Cr=C=C(NMe2)=C(NMe2)=C(CH2)5] (4) and [(CO)5Cr=C=C(Me)=C(OEt)=C(CH2)5] (5) respectively. The addition of (S)-2-methoxymethyl(N-1-propynyl)pyrrolidine (6) and (R)-methyl(1-propynyl)(1-phenylethyl)amine (8) with 1a-c leads to E/Z mixtures of [(CO)5Cr=C=C(Me)=C(R*)=C(R)R′] [R* = (S)-2-methoxymethyl pyrrolidinyl (7a-c), R* = (R)-N(Me)[CH(Me)Ph] (9a-c)]. In the reactions of 1a-c with 6 predominantly the E isomer, in the reactions of 1a-c with 8 predominantly the Z isomer is formed. All 3-amino substituted complexes exhibit a considerable solvatochromic behavior. The first hyperpolarizability β of 2b was determined by hyper-Rayleigh scattering ( β = 22 × 10-30 esu). The Kurtz powder method was used to investigate the effectiveness in second harmonic generation of 2d, 3, 7a, 7b, and 9c. Their efficiencies range from 4 to 35 times that of urea. The structures of 2b and Z-9b were established by X-ray structural analyses. Together with the results of spectroscopic investigations, they reveal a strongly delocalized π-system [(CO)5Cr=C=C=C=N].
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