Reactions of germylenes with nitrosobenzene and phenyl-t-butyl oxaziridine and its isomeric nitrone

doi:10.1016/S0022-328X(00)92342-8

Journal of Organometallic Chemistry

Volume 177, Issue 1, 11 September 1979, Pages 171-180

https://doi.org/10.1016/S0022-328X(00)92342-8 Get rights and content

Abstract

The reactions of germylenes with nitrosobenzene lead to nitrene and

intermediates via the zwitterionic form of the appropriate germaoxa-aziridines. Interactions between the germylenes and the nitrene generated in the reactions give new

-intermediates.

The formation of germaoxa-azetidine is observed in the insertion reaction of germylene into the oxaziridine ring, in the 1,3-cycloaddition of germylene to the nitrone which is an isomer of the oxaziridine and also in the dehydrochlorination reaction of C-germylated hydroxylamines

The β-elimination process from germaoxa-azetidines leads to imine and

intermediates

References (19)

H. Lavayssiere et al.
J. Organometal. Chem.
(1978)
P. Riviere et al.
J. Organometal. Chem.
(1978)
D.R. Parker et al.
J. Organometal. Chem.
(1976)
P. Riviere et al.
J. Organometal. Chem.
(1979)
P. Reviere et al.
C.R. Acad. Sci.
(1975)
G.H. Coleman et al.
Organic Synth.
(1945)
C.M. Golino et al.
J. Amer. Chem. Soc.
(1974)
D.R. Parker
Thesis, University of Californie
(1977)
J.F. Dupin
Bull. Soc. Chim. Fr.
(1967)

There are more references available in the full text version of this article.

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Germylene-transition metal complexes of the type X₂GeM(CO)₅ · THF, where M  Cr or W, X  F or Cl, react with 1,2 dipoles such as aldehydes, imines and oximes, by nucleophilic exchange at the germanium atom to form new stable adducts. Similar reactions were observed with various oxidizing agents (e.g. dimethylsulfoxide, nitrosobenzene, pyridine-N-oxide).
The high stability of the germanium-transition metal bond in these adducts impedes their decomposition into doubly bonded germanium intermediates (
, YO, NR) by methathesis.
Les réactions des complexes de métaux de transition à ligande germylène du type X₂Gem(CO)₅ · THF (M  Cr, W; X  F, Cl) avec des dipoles 1,2 (aldéhydes, imines, oximes) conduisent par échange du nucléophile porté le germanium à de nouveaux adduits stables. Des réactions similaires ont également été observées avec divers agents oxydants (diméthylsulfoxyde, nitrosobenzène et oxyde de pyridine).
Les réactions de type métathèse, conduisant à la formation de dérivés à germanium doublement lié (
, YO, NR) sont rendues assez difficiles par la grande stabilité de la liaison germanium-métal de transition dans ces complexes.
Interactions des complexes du chrome ou du tungstene a ligande germylene avec des dipoles 1,3 (nitrones, oxaziridines)
1986, Journal of Organometallic Chemistry
Transition metal-germylene complexes of the type X₂GeM(CO)₅·TMF (M  Cr, W; X  F, Cl) react with nitrones by nucleophilic exchange at gernamium to form new stable adducts. The structure of such a compound was determined by single crystal X-ray diffraction, and its bonding is discussed in terms of the resulting structural parameters.
However, reactions with oxaziridines produce unstable adducts, the decomposition products of which depend on the nature of the oxaziridine. A reaction mechanism is proposed.
Les réactions des complexes germylènes/métaux de transition du type X₂GeM(CO)₅·THF (M  Cr, W; X  F, Cl) avec des nitrones conduisent, par échange du nucléophile porté par le germanium, à de nouveaux adduits stables. La structure cristalline de l'un de ces nouveaux complexes a été déterminée par diffraction des RX. La nature des liaisons dans cet adduit est discutée à partir des paramètres structuraux.
Par contre, la réaction des oxaziridines sur ces mêmes complexes à ligande germylène conduit à des adduits instables. Leur mode de décomposition dépend de la nature de l'oxaziridine (bicyclique ou non). Un mécanisme réactionnel est également proposé.
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The fact that intermediates with silicon doubly bonded to carbon, oxygen, sulfur, nitrogen, or silicon have been described and fully characterized for several years, and no such germanium intermediate was described until 1973. Intermediates with germanium doubly bonded to carbon, oxygen, sulfur, nitrogen, phosphorus, and germanium are, like their silaanalogs, very unstable. The germanones thus generated were identified by various trapping reactions with methoxygermanes, oxagermacyclopentane, and ethylene oxide. The reactivity of azide increases with the electrophilic character of germylenes. This fact is consistent with a nucleophilic attack of azide on germylene leading to bipolar intermediate, which decomposes generating nitrogen and forming the germaimine. Germaphosphimine and silaphosphimine species with germanium or silicon doubly bonded to dicoordinated phosphorus can be obtained from 2-germa or 2- silaphosphetanes by a thermal β-decomposition reaction. In the study of GeH₂, Kraus claimed it likely that dihydride is a dimer with doubly bonded germanium atoms and that upon the addition of sodium one bond is broken to form the salt NaH₂GeGeH₂Na. The first theoretical studies on germanium doubly bonded intermediates were carried out by Gowenlock and Hunter. The instability of germanium doubly bonded intermediates makes the spectroscopic observation and measurement very difficult. Doubly bonded germanium species, as well as germylenes, are of great fundamental and practical interest. These intermediates are powerful synthetic reagents in organometallic chemistry.

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¹: Dedicated to Professor Henri Normant on the ocassion of his 72nd birthday, 25th June 1979

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Reactions of germylenes with nitrosobenzene and phenyl-t-butyl oxaziridine and its isomeric nitrone

Abstract

J. Organometal. Chem.

J. Organometal. Chem.

J. Organometal. Chem.

J. Organometal. Chem.

C.R. Acad. Sci.

Organic Synth.

J. Amer. Chem. Soc.

Thesis, University of Californie

Bull. Soc. Chim. Fr.