A 14-electron ruthenium hydride: the key intermediate in the synthesis of ruthenium carbene complexes; X-ray structure of [RuHCl(PPri3)2]

Schaaf, Paul A. van der; Kolly, Roman; Hafner, Andreas

doi:10.1039/b002298p

Cited by 31 publications

(22 citation statements)

References 17 publications

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“…Protonation of 33 and treatment with phenylacetylene gives ruthenium carbene complex 34 (Scheme 7, c). [41] A Fischer-type ruthenium carbene complex has been obtained from the same hydride 33 by treatment with ethyl vinyl ether. The primary insertion product undergoes a rearrangement to give a carbene complex that contains a hydride ligand at the ruthenium center.…”

Section: Interconversion Of Ru Carbene and Ru Hydride Speciesmentioning

confidence: 99%

Catalysis at the Interface of Ruthenium Carbene and Ruthenium Hydride Chemistry: Organometallic Aspects and Applications to Organic Synthesis

2004

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Soon after the introduction of stable and defined ruthenium precatalysts for olefin metathesis it was discovered that double bond migrations may interfere with the metathesis reaction. This undesired side reaction has been attributed to the formation of ruthenium hydride species from metathesisactive ruthenium carbene species in situ. Over the past few years, several studies have indeed revealed the existence of pathways leading from ruthenium carbene to ruthenium hydride complexes. Furthermore, a number of examples have been published recently where typical precatalysts for olefin metathesis were found to promote non-metathesis trans- Olefin Metathesis and Non-Metathesis Side ReactionsThe discovery of stable and defined carbene complexes of molybdenum [1] and ruthenium [2] as efficient precatalysts for olefin metathesis has made this transformation one of the most important CϪC bond forming reactions.[3Ϫ8]Molybdenum-based complexes such as 1 are generally [a] formations efficiently in preparatively useful yields and selectivities, presumably via the in situ formation of ruthenium hydride species. These results open up a pathway to the development of novel catalyzed reaction sequences that combine ruthenium carbene-and ruthenium-hydride-mediated steps. This paper provides an overview of the field and covers organometallic aspects as well as synthetic applications.

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Section: Interconversion Of Ru Carbene and Ru Hydride Speciesmentioning

confidence: 99%

Catalysis at the Interface of Ruthenium Carbene and Ruthenium Hydride Chemistry: Organometallic Aspects and Applications to Organic Synthesis

2004

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“…To obtain a more detailed picture of the potential-energy surface for this model system, we examined different isomers of (PH 3 ) 2 Ru(H)Cl. Special focus was put to square-planar structures as initially reported by Van der Schaaf et al [3] to determine whether these complexes are unstable intermediates or transition states. Full geometry optimizations for all structures were carried out with Gaussian 98 (Rev.…”

Section: Synthesis and Properties Of [(mentioning

confidence: 99%

“…The sawhorse structure cis-5a with the Cl trans to PH 3 turns out to be the most stable isomer, while cis-5b, with the hydride trans to PH 3 , is destabilized by 21.9 kcal mol À1 . This may easily be rationalized by the unfavorable trans arrangement of the two strong s-donors H and PH 3 . Interconversion of the model species cis-5a to its enantiomer via squareplanar transition state cis-5c, which is 42.0 kcal mol À1 higher in energy than cis-5a, is very unfavorable.…”

Section: Synthesis and Properties Of [(mentioning

confidence: 99%

“…The precipitate HNEt 3 Cl À was extracted 2 Â with THF (5 ml) and the combined THF layers were taken to dryness in vacuo. The resulting yellow-brown solid was washed with hexane (3 Â 3 ml) and then dried in vacuo.…”

Section: Experimental Partmentioning

confidence: 99%

“…An X-ray structure determination of the Ru-complex (P i Pr 3 ) 2 Ru(H)Cl (1a) by Van der Schaaf et al, describing this compound as a squareplanar complex with a trans-phosphane arrangement in the solid state, had to be revised and turned out to be a pentacoordinate N 2 -adduct [3], which had, in fact, been previously disclosed by Caulton and co-workers in an independent study [4c,e]. It still remains unclear whether the formation of the N 2 -adduct proceeds via the mononuclear hydride as an intermediate.…”

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Unsaturated Ruthenium Hydrides as Reactive Intermediates: An Experimental Investigation and Theoretical Model Study of (dtbpm-κ2P)Ru(H)Cl, (dtbpe-κ2P)Ru(H)Cl and Their Dinuclear Dynamic Precursor Complexes

Volland

Hofmann

2001

HCA

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Dedicated to the memory of Professor Luigi M. Venanzi, a gentleman, great scientist, and friend A detailed spectroscopic and quantum-chemical structure investigation of the dinuclear, 16-valenceelectron complexes [( t Bu 2 P(CH 2 ) n P t Bu 2 -k 2 P)RuH] 2 (m 2 -Cl) 2 (n 1, 2), stabilized by the bulky, electron-rich chelating ligands bis[di(t-butyl)phosphano]methane ( t Bu 2 PCH 2 P t Bu 2 , dtbpm) and 1,2-bis[di(t-butyl)phosphano]ethane ( t Bu 2 PCH 2 CH 2 P t Bu 2 , dtbpe) is reported. VT-NMR Spectroscopy of [(dtbpm-k 2 P)RuH] 2 (m 2 -Cl) 2 , an important precursor of olefin metathesis catalysts, and of its homologue [(dtbpe-k 2 P)RuH] 2 (m 2 -Cl) 2 reveals facile interconversion of dinuclear cis-and trans-dihydride isomers for both systems. Crossover experiments provide evidence for the existence of short-lived, mononuclear intermediates (dtbpm-k 2 P)Ru(H)Cl and (dtbpek 2 P)Ru(H)Cl in solution. Mechanistic features of the cis-trans isomerization process as well as structural and electronic properties of model systems for the dinuclear complexes and mononuclear intermediates were treated theoretically by DFT calculations.Introduction. ± The characterization of coordinatively and electronically unsaturated, highly reactive and therefore short-lived transition metal complexes is a matter of general interest due to the central importance of such compounds as key intermediates in various homogeneous catalytic processes [1]. Among these transient species, hydride complexes, which can catalyze hydrogenation, hydrosilylation, and hydroboration as well as CH-bond activation of organic substrates, are of particular significance. Furthermore, transition metal hydride complexes often are useful precursors in organometallic syntheses [2] and illustrate basic principles of metalÀligand bonding.Recently, there has been some experimental and theoretical controversy regarding the existence and structure of 14-electron bisphosphane Ru-hydride complexes of the type (PR 3 ) 2 Ru(H)Cl. An X-ray structure determination of the Ru-complex (P i Pr 3 ) 2 Ru(H)Cl (1a) by Van der Schaaf et al., describing this compound as a squareplanar complex with a trans-phosphane arrangement in the solid state, had to be revised and turned out to be a pentacoordinate N 2 -adduct [3], which had, in fact, been previously disclosed by Caulton and co-workers in an independent study [4c,e]. It still remains unclear whether the formation of the N 2 -adduct proceeds via the mononuclear hydride as an intermediate.

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(Alkenylalkylidene)(indenyl)ruthenium(II) Complexes: Synthesis by Protonation of Alkenyl Derivatives

Bieger

Dı́ez

Gamasa

et al. 2002

Eur. J. Inorg. Chem.

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The alkenyl complexes [Ru{(E)‐C(CO2Me)=C(H)R}(η5‐C9H7){κ2‐P,P‐(S)‐peap}] [R = CO2Me (3), H (4)], [Ru{(E)‐CH=C(H)Ph}(η5‐C9H7){κ2‐P,P‐(S)‐peap}] (5) have been prepared by reaction of the hydride complex [RuH(η5‐C9H7){κ2‐P,P‐(S)‐peap}] (2) [(S)‐peap = (−)‐(S)‐N,N‐bis(diphenylphosphanyl)(1‐phenylethyl)amine] with an equimolar amount of dimethyl acetylenedicarboxylate, or with an excess of the terminal alkynes methyl propiolate or phenylacetylene. Similarly, vinylalkenyl complexes 6a−d have been synthesized by the regio‐ and stereoselective reaction of the hydride complex 2 with 1‐ethynylcycloalkynols. Protonation of the vinylalkenyl moiety of complexes 6a,c,d with HBF4·OEt2 in diethyl ether afforded the cationic alkenylalkylidene complexes 7a−c. The structures of complexes [RuH(η5‐C9H7){κ2‐P,P‐(S)‐peap}] (2) and [Ru{(E)‐C(CO2Me)=CH(CO2Me)}(η5‐C9H7){κ2‐P,P‐(S)‐peap}] (3) have been determined by X‐ray diffraction methods. The catalytic activity of (alkenylalkylidene)(indenyl)ruthenium(II) complexes 7a−c, 8 and 9 in the ring‐closing metathesis (RCM) of diethyl diallylmalonate has been examined. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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A 14-electron ruthenium hydride: the key intermediate in the synthesis of ruthenium carbene complexes; X-ray structure of [RuHCl(PPri3)2]

Cited by 31 publications

References 17 publications

Catalysis at the Interface of Ruthenium Carbene and Ruthenium Hydride Chemistry: Organometallic Aspects and Applications to Organic Synthesis

Catalysis at the Interface of Ruthenium Carbene and Ruthenium Hydride Chemistry: Organometallic Aspects and Applications to Organic Synthesis

Unsaturated Ruthenium Hydrides as Reactive Intermediates: An Experimental Investigation and Theoretical Model Study of (dtbpm-κ2P)Ru(H)Cl, (dtbpe-κ2P)Ru(H)Cl and Their Dinuclear Dynamic Precursor Complexes

(Alkenylalkylidene)(indenyl)ruthenium(II) Complexes: Synthesis by Protonation of Alkenyl Derivatives

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