A series of rhenacyclobutadiene (RCBD) complexes Re{-C(R)=C(CO
2Et)C(OEt)=}(CO)
4 were synthesized by treatment of Na[Re(CO)
5] with
RC≡CO
2Et (R = aryl or alkyl) and ethylation reagents. The reaction of Na[Re(CO)
5]
with TMSC≡CO
2Et followed by alkylation allowed the isolation of Re{-C(TMS)=C(CO
2Et)C(OEt)=}(CO)
4 together with the isomeric complex Re{-C(CO
2Et)=C(TMS)C(OEt)=}(CO)
4. A series of amino-RCBD complexes were
obtained from reactions of alkoxy-RCBD complexes with amines.
Reactions of RCBD complexes Re{-C(R)=C(CO
2Et)C(OEt)=}(CO)
4 (R = Me, Et,
TMS) with HC≡COEt and p-HC≡CC
6H
4NMe
2 produced vinyl-substituted RCBD
complexes Re{-C(OEt)=C[C(R)=C(H)C(=O)(X)=}(CO)
4 (X = OEt, p-C
6H
4NMe
2) and
η
5-rhenacyclopetadienyl complexes Re{η
5-C
5(R)(CO
2Et)(OEt)(X)(H)}(CO)
3.
Treatment of Re{-C(TMS)=C...[
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A series of rhenacyclobutadiene (RCBD) complexes Re{-C(R)=C(CO
2Et)C(OEt)=}(CO)
4 were synthesized by treatment of Na[Re(CO)
5] with
RC≡CO
2Et (R = aryl or alkyl) and ethylation reagents. The reaction of Na[Re(CO)
5]
with TMSC≡CO
2Et followed by alkylation allowed the isolation of Re{-C(TMS)=C(CO
2Et)C(OEt)=}(CO)
4 together with the isomeric complex Re{-C(CO
2Et)=C(TMS)C(OEt)=}(CO)
4. A series of amino-RCBD complexes were
obtained from reactions of alkoxy-RCBD complexes with amines.
Reactions of RCBD complexes Re{-C(R)=C(CO
2Et)C(OEt)=}(CO)
4 (R = Me, Et,
TMS) with HC≡COEt and p-HC≡CC
6H
4NMe
2 produced vinyl-substituted RCBD
complexes Re{-C(OEt)=C[C(R)=C(H)C(=O)(X)=}(CO)
4 (X = OEt, p-C
6H
4NMe
2) and
η
5-rhenacyclopetadienyl complexes Re{η
5-C
5(R)(CO
2Et)(OEt)(X)(H)}(CO)
3.
Treatment of Re{-C(TMS)=C(CO
2Et)C(OEt)=}(CO)
4 with 4-ethynylanisole afforded
rhenium acyl complex Re{-C(=O)-C(CO
2Et)=C(TMS)-[η
2-CH=CH(p-C
6H
4OMe)]=}(CO)
4.
Reactions of RCBD complexes Re{-C(R)=C(CO
2Et)C(X)=}(CO)
4 with MeC≡CNEt
2
could produce several types of products. The η
5-rhenaoxocylcohexadienyl complexes
Re{η
5-C
6O(NEt
2)(Me)(R)(CO
2Et)(X)}(CO)
3 (R = Me, Et, TMS, X = OEt; R = Me, X
= N(CH
2)
4) were isolated as a single prodcut from the reactions of Re{-C(R)=C(CO
2Et)C(X)=}(CO)
4 with MeC≡CNEt
2. Reactions of RCBD complexes Re{-C(Ar)=C(CO
2Et)C(OEt)=}(CO)
4 (Ar = 1-naphthalenyl, 9-phenanthrenyl) with
MeC≡CNEt
2 also yielded Re{η
5-C
6O(Ar)(CO
2Et)(OEt)(Me)(NEt
2)}(CO)
3. Treatment of Re{-C(
tBu)=C(CO
2Et)C(OEt)=}(CO)
4 with MeC≡CNEt
2 generated two isomers
Re{η
5-C
6O(
tBu)(CO
2Et)(OEt)(Me)(NEt
2)}(CO)
3 and Re{η
5-
C
6O(OEt)(CO
2Et)(
tBu)(Me)(NEt
2)}(CO)
3 in a molar ratio of 1.9:1.1. These complexes
are the first structurally characterized examples of η
5-oxocyclohexadienyl complexes
containing rhenium metal. Treatment of Re{-C(R)=C(CO
2Et)C(NEt
2)=}(CO)
4 (R = Me,
Et) with MeC≡CNEt
2 yield seven-membered rhenium acyl complexes Re{-C(=O)-[η
2-
C(NEt
2)=C(Me)]-C(R)=C(CO
2Et)-C(NEt
2)=}(CO)
3. Analogous products were aslo
obtained from the reactions of Re{-C(Et)=C(CO
2Et)C(piperidinyl)=}(CO)
4 with
MeC≡CNEt
2. Additionally, vinyl-substituted RCBD complex and five-membered
oxarhenacyclic products could be isolated from the reaction of certain RCBD
complexes with MeC≡CNEt
2.
Stirring a mixture of the RCBD complexes Re{-C(Ar)=C(CO
2Et)C(OEt)=}(CO)
4 (Ar
= Ph, 1-naphthalenyl) and PhC≡CNEt
2 yielded η
5-cyclopentadienyl complexes Re{η
5-C
5(Ar)(CO
2Et)(OEt)(Ph)(NEt
2)}(CO)
3 together with η
5-oxocyclohexadienyl
complexes Re{η
5-C
6O(Ar)(CO
2Et)(OEt)(Ph)(NEt
2)}(CO)
3. The reaction of Re{-C(
tBu)=C(CO
2Et)C(OEt)=}(CO)
4 with PhC ≡ CNEt
2 gave mixture of η
5-
oxocyclohexadienyl isomeric complexes.
Reactions of Re{-C(Ar)=C(CO
2Et)C(OEt)=}(CO)
4 (Ar = Ph and 2-naphthalenyl) with
(N,N-diethylamino)allene producd mono-allene insertion heterometallabicylic
products. Reactions of RCBD complexes with (N,N-dimethylamino)allene produced
two types of rhenabicycles.
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