Cyclopentadienyl-ruthenium and -osmium chemistry. Part 20. Synthesis and X-ray structure of a cationic ruthenium–vinylidene complex, [Ru(CCHMe)(PMe3)2(η-C5H5)]PF6

Bruce, Michael I.; Wong, Fook Sin; Skelton, Brian W.; White, Allan H.

doi:10.1039/dt9820002203

Cited by 40 publications

(18 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…2) were reportedly synthesized from [CpRu(PPh 3 ) 2 Cl] (1) [Eq. (2); Cp = cyclopentadienyl], [17][18][19][20][21] stimulated a search for how such complexes may function as reactive intermediates in a catalytic cycle. These complexes are remarkably stable towards nucleophiles, for example, complex 2 must be heated at reflux in methanol to obtain the addition product.…”

Section: Additions Via Vinylidene Complexesmentioning

confidence: 99%

See 1 more Smart Citation

Ruthenium‐Catalyzed Reactions—A Treasure Trove of Atom‐Economic Transformations

2005

View full text Add to dashboard Cite

The demand for new chemicals spanning the fields of health care to materials science combined with the pressure to produce these substances in an environmentally benign fashion pose great challenges to the synthetic chemical community. The maximization of synthetic efficiency by the conversion of simple building blocks into complex targets remains a fundamental goal. In this context, ruthenium complexes catalyze a number of non-metathesis conversions and allow the rapid assembly of complex molecules with high selectivity and atom economy. These complexes often exhibit unusual reactivity. Careful consideration of the mechanistic underpinnings of the transformations can lead to the design of new reactions and the discovery of new reactivity.

show abstract

Section: Additions Via Vinylidene Complexesmentioning

confidence: 99%

“…(20)], [68] aromatic groups [Eq. (21)], [69] 1,3-dicarbonyl compounds [Eq. (22)], [70] as well as amides, amines, phosphine oxides, [67] phenols, [71] and olefins.…”

Section: Additions Via Allenylidene Complexesmentioning

confidence: 99%

Ruthenium‐Catalyzed Reactions—A Treasure Trove of Atom‐Economic Transformations

2005

View full text Add to dashboard Cite

show abstract

“…[1][2][3][4][5][6][7][8][9][10][11][12][13] While the formation of vinylidene from free ethyne is a strongly endothermic (44-47 kcal mol -1 ) process, 14,15 the relative energies of the two isomers change dramatically in the coordination sphere of several transition metals. Metal vinylidenes are stable complexes and may be more stable than the corresponding alkyne isomers.…”

Section: Introductionmentioning

confidence: 99%

Density Functional Study of Alkyne to Vinylidene Rearrangements in [(Cp)(PMe₃)₂Ru(HC⋮CR)]⁺ (R = H, Me)

Angelis

Sgamellotti

2002

Organometallics

View full text Add to dashboard Cite

The alkyne to vinylidene isomerization in [(Cp)(PMe 3 ) 2 Ru(HCtCH)] + and [(Cp)(PMe 3 ) 2 -Ru(HCtCMe)] + has been investigated by density functional calculations. For both systems, the potential energy surface for the two possible isomerization mechanisms, i.e., through a 1,2-hydrogen shift or through an oxidative addition to a hydrido-alkynyl intermediate, has been analyzed by a gradient-corrected DFT approach. The vinylidene complexes have been found more stable than the corresponding alkyne complexes, 13.1 and 10.4 kcal mol -1 , respectively, and are the thermodynamically most stable species on the potential energy surfaces of the two systems. The 1,2-hydrogen shift, proceeding via an η 2 -(C-H)-coordinated alkyne intermediate, is the energetically most favorable path for both ethyne and propyne isomerizations, with highest energy barriers of 26.8 and 18.6 kcal mol -1 , respectively. However, while the higher energy barrier computed for the oxidative addition rules out such a process in the propyne rearrangement (29.0 vs 18.6 kcal mol -1 ), the barriers for the 1,2-hydrogen shift and for the oxidative addition are almost comparable in the case of the ethyne rearrangement (26.8 vs 31.7 kcal mol -1 ), so that the oxidative addition process might become competitive. For the inverse vinylidene to propyne rearrangement we calculate an overall activation enthalpy and entropy of 25.5 kcal mol -1 and -3.0 cal K -1 mol -1 , respectively, in excellent agreement with the experimental values of 26.8 ( 0.7 kcal mol -1 and -4.9 ( 1.9 cal K -1 mol -1 .

show abstract

“…2) aus [CpRu(PPh 3 ) 2 Cl] (1) [Gl. (2); Cp = Cyclopentadienyl]; [17][18][19][20][21] dies führte zu der Frage, wie solche Komplexe als reaktive Zwischenstufen in einem Katalysezyklus fungieren können. Die Komplexe sind gegen Nucleophile bemerkenswert stabil: Beispielsweise muss Komplex 2 in Methanol unter Rückfluss erhitzt werden, um das Additionsprodukt zu erhalten.…”

Section: Additionen üBer Vinyliden-komplexeunclassified

“…(21)], [69] 1,3-Dicarbonylverbindungen [Gl. (22)] [70] sowie Amiden, Aminen, Phosphinoxiden, [67] Phenolen [71] und Olefinen.…”

Section: Additionen üBer Allenyliden-komplexeunclassified

Ruthenium‐katalysierte Reaktionen – eine Schatzkiste für atomökonomische Umwandlungen

2005

View full text Add to dashboard Cite

Der stetige Bedarf an neuen Chemikalien bei gleichzeitiger Forderung nach umweltfreundlichen Herstellungsmethoden stellt an Synthesechemiker große Anforderungen. Die Maximierung der Syntheseeffizienz durch die Umwandlung einfacher Bausteine in komplexe Zielmoleküle bleibt daher eine grundlegende Aufgabe. In diesem Zusammenhang ist die Verwendung von Ruthenium‐Komplexen als Katalysatoren für mehrere nichtmetathetische Umwandlungen ein vielversprechender Ansatz, denn diese Komplexe ermöglichen den schnellen Aufbau komplexer Moleküle mit hoher Selektivität und Atomökonomie. Zudem zeigen sie häufig ungewöhnliche Reaktivität, und durch das sorgfältige Studium der zugrundeliegenden Mechanismen können neue Reaktionen entwickelt und neue Reaktivitäten entdeckt werden.

show abstract

Cyclopentadienyl-ruthenium and -osmium chemistry. Part 20. Synthesis and X-ray structure of a cationic ruthenium–vinylidene complex, [Ru(CCHMe)(PMe₃)₂(η-C₅H₅)]PF₆

Abstract: Die kationischen Vinyliden‐Ru‐Komplexe (II) werden durch die Reaktion des neutralen Chloro‐Ru(II)‐Komplexes (I) mit entsprechenden Alkinen und Ammoniumhexafluorophosphat synthetisiert.

Cited by 40 publications

References 2 publications

Ruthenium‐Catalyzed Reactions—A Treasure Trove of Atom‐Economic Transformations

Ruthenium‐Catalyzed Reactions—A Treasure Trove of Atom‐Economic Transformations

Density Functional Study of Alkyne to Vinylidene Rearrangements in [(Cp)(PMe₃)₂Ru(HC⋮CR)]⁺ (R = H, Me)

Ruthenium‐katalysierte Reaktionen – eine Schatzkiste für atomökonomische Umwandlungen

Contact Info

Product

Resources

About

Cyclopentadienyl-ruthenium and -osmium chemistry. Part 20. Synthesis and X-ray structure of a cationic ruthenium–vinylidene complex, [Ru(CCHMe)(PMe3)2(η-C5H5)]PF6

Abstract: Die kationischen Vinyliden‐Ru‐Komplexe (II) werden durch die Reaktion des neutralen Chloro‐Ru(II)‐Komplexes (I) mit entsprechenden Alkinen und Ammoniumhexafluorophosphat synthetisiert.

Cited by 40 publications

References 2 publications

Ruthenium‐Catalyzed Reactions—A Treasure Trove of Atom‐Economic Transformations

Ruthenium‐Catalyzed Reactions—A Treasure Trove of Atom‐Economic Transformations

Density Functional Study of Alkyne to Vinylidene Rearrangements in [(Cp)(PMe3)2Ru(HC⋮CR)]+ (R = H, Me)

Ruthenium‐katalysierte Reaktionen – eine Schatzkiste für atomökonomische Umwandlungen

Contact Info

Product

Resources

About

Cyclopentadienyl-ruthenium and -osmium chemistry. Part 20. Synthesis and X-ray structure of a cationic ruthenium–vinylidene complex, [Ru(CCHMe)(PMe₃)₂(η-C₅H₅)]PF₆

Density Functional Study of Alkyne to Vinylidene Rearrangements in [(Cp)(PMe₃)₂Ru(HC⋮CR)]⁺ (R = H, Me)