Study of the Interaction of [Ru(C5H5)Cl(dippe)] and [Ru(C5Me5)Cl(dippe)] with Dihydrogen, Dinitrogen, and Other Small Molecules. X-ray Crystal Structures of

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• 作者：Isaac de los Rí ; os ; Manuel Jimé ; nez Tenorio ; Jaime Padilla ; M. Carmen Puerta ; and Pedro Valerga
• 刊名：Organometallics
• 出版年：1996
• 出版时间：October 15, 1996
• 年：1996
• 卷：15
• 期：21
• 页码：4565 - 4574
• 全文大小：281K
• 年卷期：v.15,no.21(October 15, 1996)
• ISSN：1520-6041

文摘

The complexes [CpRuCl(dippe)] and [Cp*RuCl(dippe)](Cp = C₅H₅; Cp* =C₅Me₅; dippe =1,2-bis(diisopropylphosphino)ethane) react withH₂ and Na[BPh₄] in EtOH or MeOHtofurnish the dihydrides[CpRuH₂(dippe)][BPh₄](1) and[Cp*RuH₂(dippe)][BPh₄](2). Thesecompounds are deprotonated by KOBu^t to yield themonohydrides [CpRuH(dippe)] (3) and[Cp*RuH(dippe)] (4), which can be protonated back byHBF₄·OEt₂ at low temperaturestogive the dihydrogen adducts[CpRu(H₂)(dippe)][BF₄](5) and[Cp*Ru(H₂)(dippe)][BF₄](6).These compounds rearrange irreversibly to the dihydride form asthe temperature is raised.A kinetic study of these rearrangement processes suggests that theisomerization mechanismis different in each case. The dinitrogen complex[CpRu(N₂)(dippe)][BPh₄] (7)and the acetoneadduct[CpRu(Me₂CO)(dippe)][BPh₄](8) were obtained by reaction of [CpRuCl(dippe)]withAg⁺ in acetone under dinitrogen or argon, respectively,followed by NaBPh₄/EtOH. Bothcompounds react with atmospheric oxygen yielding[CpRu(⁶-C₆H₅BPh₃)](9) andⁱPr₂P(O)CH₂CH₂P(O)ⁱPr₂. Thedinitrogen adduct[Cp*Ru(N₂)(dippe)][BPh₄](10) was also obtained, butit reacts irreversibly with traces of O₂ to give thedioxygen complex[Cp*Ru(O₂)(dippe)][BPh₄],previously known. A range of neutral donors L also react with[CpRuCl(dippe)] or [Cp*RuCl(dippe)] and NaBPh₄ furnishing the corresponding complexes[CpRu(L)(dippe)][BPh₄] (L=CO (11), CNBu^t (12),C₂H₄ (13)), or[Cp*Ru(L)(dippe)][BPh₄] (L = CO(14), CNBu^t (15),C₂H₄(16)). The ethylene adduct 16 is only stableunder an ethylene atmosphere, whereas 13 isa stable species. The X-ray crystal structures of compounds2, 12, and 13 are alsoreported.