Details
| Originalsprache | Englisch |
|---|---|
| Seiten (von - bis) | 175-186 |
| Seitenumfang | 12 |
| Fachzeitschrift | Inorganica chimica acta |
| Jahrgang | 220 |
| Ausgabenummer | 1-2 |
| Publikationsstatus | Veröffentlicht - Juni 1994 |
| Extern publiziert | Ja |
Abstract
Tricarbonyl(η6-1-oxobenzocyclobutene)chromium(0) (1) can be transformed to tricarbonyl(η6-1-endo-hydroxybenzocyclobutene) chromium(0) derivatives with substituents R (RCH3, CHCH2, (CH2)4CHCH2, (CH2)4OSi(Me)2tBu) at Cl on the exo face of the complex. The relative configuration is proven by an X-ray crystal structure analysis of the trimethylsilyl ether 8 (C16H18CrO4Si: a=8.693(1), b=9.490(1), c=11.063(1) Å, α=97.51(1), β=110.32(1), γ=95.38(1)°, triclinic, space group P1(No.2), R=0.037, Rw=0.052 for 4609 observed reflections. Attempts directed at an intramolecular cycloaddition of the ortho-quinodimethane complex derived from 17 by anion promoted ring opening unexpectedly resulted in the formation of 12 as the product of an opening of the proximal bond of the anellated ring located between the hydroxy group and the coordinated aromatic ring in 16. The fact that the intermolecular cycloaddition reaction for 16 is possible in the presence of a dienophile is taken as evidence for an equilibrium between the alcoholate 17 and the two ring opened products 16 and 18. The proximal ring opening of 6 is not observed when the free organic ligand 21 is used as the educt. Ketone complexes 1 and 25 undergo proximal ring opening reaction when treated with alcoholate or primary amines.
ASJC Scopus Sachgebiete
- Chemie (insg.)
- Physikalische und Theoretische Chemie
- Chemie (insg.)
- Anorganische Chemie
- Werkstoffwissenschaften (insg.)
- Werkstoffchemie
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in: Inorganica chimica acta, Jahrgang 220, Nr. 1-2, 06.1994, S. 175-186.
Publikation: Beitrag in Fachzeitschrift › Artikel › Forschung › Peer-Review
}
TY - JOUR
T1 - Reactions of benzocyclobutene chromium complexes with carbon, nitrogen and oxygen nucleophiles
T2 - nucleophilic addition and unexpected proximal ring opening reactions
AU - Brands, Michael
AU - Wey, Hans G.
AU - Goddard, Richard
AU - Butenschön, Holger
N1 - Funding information: The authorst hank the Max-Planck-Gesellschaftt,h e Deutsche Forschungsgemeinschaftt,h e Volkswagen-Stiftung and the Fonds der ChemischenI ndustrie for their support.
PY - 1994/6
Y1 - 1994/6
N2 - Tricarbonyl(η6-1-oxobenzocyclobutene)chromium(0) (1) can be transformed to tricarbonyl(η6-1-endo-hydroxybenzocyclobutene) chromium(0) derivatives with substituents R (RCH3, CHCH2, (CH2)4CHCH2, (CH2)4OSi(Me)2tBu) at Cl on the exo face of the complex. The relative configuration is proven by an X-ray crystal structure analysis of the trimethylsilyl ether 8 (C16H18CrO4Si: a=8.693(1), b=9.490(1), c=11.063(1) Å, α=97.51(1), β=110.32(1), γ=95.38(1)°, triclinic, space group P1(No.2), R=0.037, Rw=0.052 for 4609 observed reflections. Attempts directed at an intramolecular cycloaddition of the ortho-quinodimethane complex derived from 17 by anion promoted ring opening unexpectedly resulted in the formation of 12 as the product of an opening of the proximal bond of the anellated ring located between the hydroxy group and the coordinated aromatic ring in 16. The fact that the intermolecular cycloaddition reaction for 16 is possible in the presence of a dienophile is taken as evidence for an equilibrium between the alcoholate 17 and the two ring opened products 16 and 18. The proximal ring opening of 6 is not observed when the free organic ligand 21 is used as the educt. Ketone complexes 1 and 25 undergo proximal ring opening reaction when treated with alcoholate or primary amines.
AB - Tricarbonyl(η6-1-oxobenzocyclobutene)chromium(0) (1) can be transformed to tricarbonyl(η6-1-endo-hydroxybenzocyclobutene) chromium(0) derivatives with substituents R (RCH3, CHCH2, (CH2)4CHCH2, (CH2)4OSi(Me)2tBu) at Cl on the exo face of the complex. The relative configuration is proven by an X-ray crystal structure analysis of the trimethylsilyl ether 8 (C16H18CrO4Si: a=8.693(1), b=9.490(1), c=11.063(1) Å, α=97.51(1), β=110.32(1), γ=95.38(1)°, triclinic, space group P1(No.2), R=0.037, Rw=0.052 for 4609 observed reflections. Attempts directed at an intramolecular cycloaddition of the ortho-quinodimethane complex derived from 17 by anion promoted ring opening unexpectedly resulted in the formation of 12 as the product of an opening of the proximal bond of the anellated ring located between the hydroxy group and the coordinated aromatic ring in 16. The fact that the intermolecular cycloaddition reaction for 16 is possible in the presence of a dienophile is taken as evidence for an equilibrium between the alcoholate 17 and the two ring opened products 16 and 18. The proximal ring opening of 6 is not observed when the free organic ligand 21 is used as the educt. Ketone complexes 1 and 25 undergo proximal ring opening reaction when treated with alcoholate or primary amines.
KW - Benzocyclobutenedione complexes
KW - Benzocyclobutenone complexes
KW - Chromium complexes
KW - Crystal structures
KW - Ring opening
UR - http://www.scopus.com/inward/record.url?scp=0000768148&partnerID=8YFLogxK
U2 - 10.1016/0020-1693(94)03870-8
DO - 10.1016/0020-1693(94)03870-8
M3 - Article
AN - SCOPUS:0000768148
VL - 220
SP - 175
EP - 186
JO - Inorganica chimica acta
JF - Inorganica chimica acta
SN - 0020-1693
IS - 1-2
ER -