Hydrocarbon complexes of ruthenium. Part IV. Cyclic dienyl complexes
- 1 January 1975
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 16-17,p. 1633-1640
- https://doi.org/10.1039/dt9750001633
Abstract
Cyclopentadiene, cyclohexa-1,3-diene, and cyclohepta-1,3-diene yield dienyl complexes [Ru(MMe3)(CO)2(1–5-η-dienyl)](M = Si or Ge) on reaction with [Ru(MMe3)2(CO)4](M = Si or Ge) or [{Ru(SiMe3)(CO)4}2]. Cyclohexa-1,3-diene gives [Ru(CO)3(1–2 : 3–4 η-C6H8)] as the major product with both ruthenium complexes, whereas Cyclopentadiene and cyclohepta-1,3-diene give the corresponding [Ru(CO)3(1–2 : 3–4-η-diene)] complex only with [{Ru(SiMe3)(CO)4}2]. In the Cyclopentadiene reactions, formation of [Ru(CO)3(1–2 : 3–4-η-C5H6)] is deduced from observation of its decomposition product [RuH(CO)2(η-C5H5)]. Both [Ru(CO)3-(1–2 : 3–4-η-C6H8)] and [Ru(CO)3(1–2 : 3–4-η-C7H10)] are best prepared by treating Ru3(CO)12 with the diene, and have been employed as source of the cations [Ru(CO)3(1–5-η-C6H7)]+ and [Ru(CO)3(1–5-η-C7H9)]+via hydride abstract ion with [Ph3C][BF4]. The interaction of the cations with several nucleophiles has been studied, revealing a wide variation in the site of attack. Thus X–(X = Br or I), CN–, OMe–, and H– attack [Ru(CO)3(1–5-η-C7H9)]+ to yield respectively [RuX(CO)2(1–5-η-C7H9)], [Ru(CO)3(1-σ,3–5-η-C7H9CN-2)], [Ru(CO)3-(1–2 : 3–4-η-C7H9OMe-5)], and a mixture of [Ru(CO)3(1-σ,3–5-η-C7H10)] and [Ru(CO)3(1–2 : 3–4-η-C7H10)].Keywords
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