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Preparation and characterization of 4-azoniaheptatrienyl, 4-azaheptatrienyl, ruthenapyrrolinone, and pyrrolinyl complexes of ruthenium

AuthorsBuil, María L. ; Esteruelas, Miguel A. ; López, Ana M. ; Oñate, Enrique
Issue Date2003
PublisherAmerican Chemical Society
CitationOrganometallics 22(25): 5274-5284 (2003)
AbstractThe allenylidene complex [Ru(η5-C5H 5)(=C=C=CPh2)(CO)(PiPr3)]BF 4 (1) adds the N-H bond of diallylamine to afford the N-allyl-4-azonia-1,3,6-heptatrienyl derivative [Ru(η5-C 5H5)-{C(CH=CPh2)=N(CH2CH=CH 2)2}(CO)(PiPr3)]BF4 (2). Treatment of 2 with sodium methoxide in tetrahydrofuran produces the deprotonation of the NCH2 group of one of the allyl groups and the formation of a 1:1 mixture of the ruthenapyrrolinone complex (R Ru,RC- SRu,SC)-Ru(η 5-C5H5)[=C(CH=CPh2)=N(CH 2CH=CH2)CH(CH=CH2)C=O}(PiPr 3) (3) and the pyrrolinyl compound (RRu,SC- SRu,RC)-Ru(η5-C5H 5){C=CHCPh2CH(CH=CH2)NCH2CH=CH 2}-(CO)(PiPr3) (4). Protonation of 4 with HBF4·OEt2 in diethyl ether initially leads to the heterocyclic derivative (RRu,SC- SRu,R C)-[Ru(η5-C5H5){C=N(CH 2CH=CH2)CH(CH=CH2)-CPh2CH 2}(CO)(PiPr3)BF4 (5), containing a C-N double bond. In dichloromethane, complex 5 is unstable and evolves into the N-allyl-4-azonia-1,3,5-heptatrienyl complex [Ru(η5-C 5H5)-{C(CH=CPh2)=N(CH=CHCH3)CH 2CH=CH2}(CO)(PiPr3)]BF4 (6). The process involves the opening of the five-membered heterocycle and a proton transfer from the -CH2CN- group to the =CH2 carbon atom of the vinyl substituent of the heterocycle. Complex 1 also reacts with allylamine. The reaction leads to the 4-azonia-1,3,6-heptatrienyl derivative [Ru(η5-C5H5){C(CH=CPh 2)=NH(CH2CH=CH2)}(CO)(PiPr 3)]BF4 (7). In contrast to 2, the deprotonation of 7 with sodium methoxide in tetrahydrofuran takes place at the nitrogen atom. In toluene at 70 °C, the resulting 4-aza-1,3,6-heptatrienyl complex Ru(η5-C5H5){C(CH=CPh2)=NCH 2CH=CH2}(CO)(PiPr3) (8) isomerizes into the conjugated 4-aza-1,3,5-heptatrienyl derivative Ru(η 5-C5H5){C(CH=CPh2)=NCH=CHCH 3}(CO)(PiPr3) (9), as a result of a 1,3-sigmatropic rearrangement in the allyl unit. Complexes 3, 4, 5, and 9 have been characterized by X-ray diffraction analysis.
Identifiersdoi: 10.1021/om030518m
issn: 0276-7333
e-issn: 1520-6041
Appears in Collections:(ICMA) Artículos
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