Reactions of Enimines with [Cp*RuCl]4: Half-Open Ruthenocene and Related Species Incorporating Heteroatoms

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• 作者：J. Alfredo Gutierrez ; Ma. Elena Navarro Clemente ; M. Angeles Paz-Sandoval ; Atta M. Arif ; and Richard D. Ernst
• 刊名：Organometallics
• 出版年：1999
• 出版时间：March 15, 1999
• 年：1999
• 卷：18
• 期：6
• 页码：1068 - 1079
• 全文大小：250K
• 年卷期：v.18,no.6(March 15, 1999)
• ISSN：1520-6041

文摘

The reactions of enimines and various silicon, germanium, and tin derivatives with[Cp*RuCl]₄ have been investigated and found to lead to a variety of products, depending onthe nature of the enimine and the reaction conditions. In general, mixtures of products wereobtained comprised of Cp*Ru(⁵-azadienyl), Cp*Ru(³-azadienyl)Cl₂, and Cp*Ru(⁴-amino-1,3-diene)Cl complexes. Significant differences in both product preferences and overall yieldswere observed between the silicon, germanium, and tin reagents, the last typically favoringthe ⁵ complexes. The choice of solvent also played a major role, the ⁵ complex being slightlyto somewhat disfavored in THF relative to benzene. An attempt to convert an ⁴-aminodienecomplex, Cp*Ru[⁴-CH₃CHCHC(CH₃)CHNH(t-Bu)], to an ⁵-azadienyl complex throughreaction with Ag⁺ in the presence of K₂CO₃ led to a mixture of species, which included thedesired ⁵ complex as well as an unusual Cp*Ru(³-dienimine)Cl species, which arose froma formal two-electron oxidation followed by two deprotonations, from the nitrogen centerand the internal methyl group. Coordination in this species occurs through the nitrogencenter and the distal olefin. Structural confirmation for this species, as well as for one ⁴and three ⁵ complexes, has been obtained.