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

被引：34

作者：

Buil, ML ^{[1
]}

Esteruelas, MA ^{[1
]}

López, AM ^{[1
]}

Oñate, E ^{[1
]}

机构：

[1] Univ Zaragoza, CSIC, Inst Ciencia Mat Aragon, Dept Quim Inorgan, E-50009 Zaragoza, Spain

来源：

ORGANOMETALLICS | 2003年 / 22卷 / 25期

关键词：

D O I：

10.1021/om030518m

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The allenylidene complex [Ru(eta(5)-C5H5)(=C=C=CPh2)(CO)(PiPr(3))]BF4 (1) adds the N-H bond of diallylamine to afford the N-allyl-4-azonia-1,3,6-heptatrienyl derivative [Ru(eta(5)-C5H5)-{C(CH CPh2)=N(CH2CH=CH2)(2)}(CO)(PiPr(3))]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,R-C- S-Ru,S-C)-Ru(eta(5)-C5H5)[=C(CH=CPh2)-N(CH2CH=CH2)CH(CH=CH2)C=O}((PPr3)-Pr-i) rolinyl compound (R-Ru,S-C- S-Ru,R-C)-Ru(eta(5) -C5H5){C=CHCPh2CH(CH=CH2)NCH2CH=CH2]-(CO)((PPr3)-Pr-i) (4). Protonation of 4 with HBF4.OEt2 in diethyl ether initially leads to the heterocyclic derivative (R-Ru,S-C- S-Ru,R-C)-[Ru(eta(5)-C5H5){C=N(CH2CH=CH2)CH(CH=CH2)-CPh2CH2}(CO)((PPr3)-Pr-i)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(eta(5)-C5H5)-{C(CH=CPh2)=N(CH=CHCH3)CH2CH=CH2}(CO)((PPr3)-Pr-i)]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(eta(5)-C5H5){C(CH=CPh2)=NH(CH2CH=CH2)}(CO)((PPr3)-Pr-i)]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 degreesC, the resulting 4-aza-1,3,6-heptatrienyl complex Ru(eta(5)-C5H5){C(CH=CPh2)=NCH2CH=CH2}(CO)((PPr3)-Pr-i) (8) isomerizes into the conjugated 4-aza-1,3,5-heptatrienyl derivative Ru(eta(5)-C5H5){C(CH=CPh2)=NCH=CHCH3}(CO)((PPr3)-Pr-i) (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.

引用

页码：5274 / 5284

页数：11

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