Synthesis, X-ray Structure, and Reactivity of Phosphine-Substituted Iron Carbonyl Complexes Containing <i>σ</i>-Alkyl−<i>π</i>-Allyl Ligands

Jenny, Titus A.; Huber, V.; Ma, Liqian; Raemy, J.; Zeller, David; Stœckli-Evans, Helen

doi:10.1021/om010781s

Cited by 6 publications

(1 citation statement)

References 26 publications

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“…Impressively, in 1975, the authors characterised their products and suggested a reaction mechanism solely on the basis of their NMR data (at 60 MHz) and mass spectra [85]. Gratifyingly, their proposals were fully vindicated almost three decades later by the isolation and X-ray crystallographic structural determination of the π-allyl/σ-alkyl intermediate, 161 (Figure 4) [86]. Impressively, in 1975, the authors characterised their products and suggested a reaction mechanism solely on the basis of their NMR data (at 60 MHz) and mass spectra [85].…”

Section: Interactions Of Ring-strained Terpenes With Organometallic R...mentioning

confidence: 99%

Organotransition Metal Chemistry of Terpenes: Syntheses, Structures, Reactivity and Molecular Rearrangements

McGlinchey

2024

Molecules

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The impact of organometallic chemistry on the terpene field only really blossomed in the 1960s and 1970s with the realisation that carbon–carbon bond formation under mild conditions could be achieved by using nickel or iron carbonyls as synthetic reagents. Concomitantly, the development of palladium derivatives capable of the controlled coupling of isoprene units attracted the attention of numerous highly talented researchers, including future Nobel laureates. We discuss briefly how early work on the syntheses of simple monoterpenes soon progressed to sesquiterpenes and diterpenes of increasing complexity, such as humulene, flexibilene, vitamin A, or pheromones of commercial value, in particular those used in perfumery (muscone, lavandulol), or grandisol and red scale pheromone as replacements for harmful pesticides. As the field progressed, there has been more emphasis on developing organometallic routes to enantiopure rather than racemic products, as well as gaining precise mechanistic data on the transformations, notably the course of metal-promoted molecular rearrangements that have long been a feature of terpene chemistry. We note the impact of the enormously enhanced analytical techniques, high-field NMR spectroscopy and X-ray crystallography, and their use to re-examine the originally proposed structures of terpenes and their organometallic derivatives. Finally, we highlight the very recent ground-breaking use of the crystalline sponge method to acquire structural data on low-melting or volatile terpenes. The literature cited herein covers the period 1959 to 2023.

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Section: Interactions Of Ring-strained Terpenes With Organometallic R...mentioning

confidence: 99%

Organotransition Metal Chemistry of Terpenes: Syntheses, Structures, Reactivity and Molecular Rearrangements

McGlinchey

2024

Molecules

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The Chemistry of Iron–Alkyl Complexes

Alberch

Ulicki

Asad

et al. 2013

Patai's Chemistry of Functional Groups

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Iron‐alkyl complexes are found as intermediates in a variety of homogenous organometallic reactions. The chapter deals with the synthesis, stability and reactions of iron‐alkyl complexes. Wilkinson and Piper in 1956 were the first to report an iron‐alkyl complex, and these investigations lead to the discovery of a whole range of reactions involving these complexes. This chapter will firstly cover the preparation of iron‐alkyl complexes, followed by the main categories of reactions in which these complexes take part, mainly CO insertion reactions and electrophilic cleavage reactions. A brief account of the role of FpMe (Fp = CpFe(CO) 2 ) complexes in catalytic processes are also included in this chapter.

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Syntheses of η¹‐Alkyl‐η³‐Allyl‐η⁵‐Cyclopentadienyl Cobalt(III) Complexes and Their Use in Low‐temperature Atomic Layer Deposition of Cobalt‐Containing Thin Films

Lü

Zhu

Wang

et al. 2023

Chemistry A European J

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Herein, we report the design and scalable synthesis of three new Co(III) complexes, which have an unusual hydrocarbon η1‐alkyl‐η3‐allyl‐η5‐cyclopentadienyl ligation structure, from the reactions of readily available cobalt(II) compound CoCl2(PPh3)2 and biomass material β‐pinene via C−C bond activation. These Co(III) complexes are air‐stable, fairly volatile, and thermally stable, so they are excellent candidates as the metal precursors for the vapor deposition of cobalt‐containing thin films. As a demonstration, we show that the Co(III) complex of [(3’‐5’‐η,1‐σ)‐methylene(2,2,4‐trimethyl‐4‐cyclohexene‐1,3‐diyl)](η5‐methylcyclopentadienyl)Co (i. e. (seco‐pinene)(MeCp)Co) is well suited for the atomic layer deposition (ALD) of Co3O4 and CoS2 thin films, and the deposited Co3O4 and CoS2 films are able to conformally cover trench structures with a fairly high aspect ratio of 10 : 1.

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Synthesis, X-ray Structure, and Reactivity of Phosphine-Substituted Iron Carbonyl Complexes Containing σ-Alkyl−π-Allyl Ligands

Cited by 6 publications

References 26 publications

Organotransition Metal Chemistry of Terpenes: Syntheses, Structures, Reactivity and Molecular Rearrangements

Organotransition Metal Chemistry of Terpenes: Syntheses, Structures, Reactivity and Molecular Rearrangements

The Chemistry of Iron–Alkyl Complexes

Syntheses of η¹‐Alkyl‐η³‐Allyl‐η⁵‐Cyclopentadienyl Cobalt(III) Complexes and Their Use in Low‐temperature Atomic Layer Deposition of Cobalt‐Containing Thin Films

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Synthesis, X-ray Structure, and Reactivity of Phosphine-Substituted Iron Carbonyl Complexes Containing σ-Alkyl−π-Allyl Ligands

Cited by 6 publications

References 26 publications

Organotransition Metal Chemistry of Terpenes: Syntheses, Structures, Reactivity and Molecular Rearrangements

Organotransition Metal Chemistry of Terpenes: Syntheses, Structures, Reactivity and Molecular Rearrangements

The Chemistry of Iron–Alkyl Complexes

Syntheses of η1‐Alkyl‐η3‐Allyl‐η5‐Cyclopentadienyl Cobalt(III) Complexes and Their Use in Low‐temperature Atomic Layer Deposition of Cobalt‐Containing Thin Films

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Syntheses of η¹‐Alkyl‐η³‐Allyl‐η⁵‐Cyclopentadienyl Cobalt(III) Complexes and Their Use in Low‐temperature Atomic Layer Deposition of Cobalt‐Containing Thin Films