Terminal alkynes (HCdropCR') (R'=COOMe, CH2OH) insert into the metal-carbyne bond of the diiron complexes [Fe-2{mu-CN(Me)(R)} (mu-CO)(CO)(NCMe)(Cp)(2)][SO3CF3] (R=Xyl, 1a; CH2Ph, 1b; Me, 1c; Xyl=2,6-Me2C6H3), affording the corresponding mu-vinyliminium complexes [Fe-2{mu-sigma:eta(3)-C(R')=CHC=N(Me)(R)}(mu-CO)(CO)(Cp)(2)][SO3CF3] (R=Xyl, R'=COOMe, 2; R=CH2Ph, R'=COOMe, 3; R=Me, R'=COOMe, 4; R=Xyl, R'=CH2OH, 5; R=Me, R'=CH2OH, 6). The insertion is regiospecific and C-C bond formation selectively occurs between the carbyne carbon and the CH moiety of the alkyne. Disubstituted alkynes (R'CdropCR') also insert into the metal-carbyne bond leading to the formation of [Fe-2{mu-sigma:eta(3)- C(R')=C(R')C=N(Me)(R)}(mu-CO)(CO)(Cp)(2)][SO3CF3] (R'=Me, R=Xyl, 8; R'=Et, R=Xyl, 9; R'=COOMe, R=Xyl, 10; R'=COOMe, R=CH2Ph, 11; R'= COOMe, R=Me, 12). Complexes 2, 3, 5, 8, 9 and 11, in which the iminium nitrogen is unsymmetrically substituted, give rise to E and/or Z isomers. When iminium substituents are Me and Xyl, the NMR and structural investigations (X-ray structure analysis of 2 and 8) indicate that complexes obtained from terminal alkynes preferentially adopt the E configuration, whereas those derived from internal alkynes are exclusively Z. In complexes 8 and 9, trans and cis isomers have been observed, by NMR spectroscopy, and the structures of trans-8 and cis-8 have been determined by X-ray diffraction studies. Trans to cis isomerization occurs upon heating in THF at reflux temperature. In contrast to the case of HCdropCR', the insertion of 2-hexyne is not regiospecific: both [Fe-2{mu-sigma:eta(3)-C(CH2CH2CH3)=C(Me)C=N(Me)(R)} (mu-CO)(CO)(Cp)(2)][SO3CF3] (R=Xyl, 13; R=Me, 15) and [Fe-2{mu-sigma:eta(3)-C(Me)=C(CH2CH2CH3)C=N(Me)(R)}(mu-CO)(CO)(Cp)(2)][SO3CF3] (R=Xyl, 14, R=Me, 16) are obtained and these compounds are present in solution as a mixture of cis and trans isomers, with predominance of the former.

Stereochemistry of the insertion of disubstituted alkynes into the metal aminocarbyne bond in diiron complexes

MARCHETTI, FABIO;
2004

Abstract

Terminal alkynes (HCdropCR') (R'=COOMe, CH2OH) insert into the metal-carbyne bond of the diiron complexes [Fe-2{mu-CN(Me)(R)} (mu-CO)(CO)(NCMe)(Cp)(2)][SO3CF3] (R=Xyl, 1a; CH2Ph, 1b; Me, 1c; Xyl=2,6-Me2C6H3), affording the corresponding mu-vinyliminium complexes [Fe-2{mu-sigma:eta(3)-C(R')=CHC=N(Me)(R)}(mu-CO)(CO)(Cp)(2)][SO3CF3] (R=Xyl, R'=COOMe, 2; R=CH2Ph, R'=COOMe, 3; R=Me, R'=COOMe, 4; R=Xyl, R'=CH2OH, 5; R=Me, R'=CH2OH, 6). The insertion is regiospecific and C-C bond formation selectively occurs between the carbyne carbon and the CH moiety of the alkyne. Disubstituted alkynes (R'CdropCR') also insert into the metal-carbyne bond leading to the formation of [Fe-2{mu-sigma:eta(3)- C(R')=C(R')C=N(Me)(R)}(mu-CO)(CO)(Cp)(2)][SO3CF3] (R'=Me, R=Xyl, 8; R'=Et, R=Xyl, 9; R'=COOMe, R=Xyl, 10; R'=COOMe, R=CH2Ph, 11; R'= COOMe, R=Me, 12). Complexes 2, 3, 5, 8, 9 and 11, in which the iminium nitrogen is unsymmetrically substituted, give rise to E and/or Z isomers. When iminium substituents are Me and Xyl, the NMR and structural investigations (X-ray structure analysis of 2 and 8) indicate that complexes obtained from terminal alkynes preferentially adopt the E configuration, whereas those derived from internal alkynes are exclusively Z. In complexes 8 and 9, trans and cis isomers have been observed, by NMR spectroscopy, and the structures of trans-8 and cis-8 have been determined by X-ray diffraction studies. Trans to cis isomerization occurs upon heating in THF at reflux temperature. In contrast to the case of HCdropCR', the insertion of 2-hexyne is not regiospecific: both [Fe-2{mu-sigma:eta(3)-C(CH2CH2CH3)=C(Me)C=N(Me)(R)} (mu-CO)(CO)(Cp)(2)][SO3CF3] (R=Xyl, 13; R=Me, 15) and [Fe-2{mu-sigma:eta(3)-C(Me)=C(CH2CH2CH3)C=N(Me)(R)}(mu-CO)(CO)(Cp)(2)][SO3CF3] (R=Xyl, 14, R=Me, 16) are obtained and these compounds are present in solution as a mixture of cis and trans isomers, with predominance of the former.
ALBANO V., G; Busetto, L; Marchetti, Fabio; Monari, M; Zacchini, S; Zanotti, V.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11568/187971
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