Arene transition metal chemistry

Muetterties, E. L.; Bleeke, John R.; Sievert, Allen C.

doi:10.1016/s0022-328x(00)87871-7

Cited by 108 publications

(34 citation statements)

References 46 publications

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“…The binary phase of the formal composition “K 4 Pb 9 ” was prepared by high‐temperature reaction (350 °C) from the elements K and Pb in the ratio of 4:9. [MesMo(CO) 3 ] was prepared by heating [Mo(CO) 6 ] (Alfa Inorganics) in an excess of mesitylene under reflux in a nitrogen atmosphere 29…”

Section: Methodsmentioning

confidence: 99%

[Pb₅{Mo(CO)₃}₂]⁴⁻: A Complex Containing a Planar Pb₅ Unit

Hoffmann

Fässler

et al. 2005

Angew Chem Int Ed

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Lead around: The cyclic [Pb5]4− ion can be stabilized as an organometallic complex with the {Mo(CO)3} fragment. This complex is formed by the reaction of [Pb9]4− with [MesMo(CO)3] (Mes=1,3,5‐trimethylbenzene). In the solid state this highly charged anion forms a linear chain with strong interactions between the potassium cations and the carbonyl oxygen atoms (see picture; cyan Mo, purple K, and red Pb; C and O atoms are omitted).

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Section: Methodsmentioning

confidence: 99%

[Pb₅{Mo(CO)₃}₂]⁴⁻: A Complex Containing a Planar Pb₅ Unit

Hoffmann

Fässler

et al. 2005

Angew Chem Int Ed

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“…The finding that arene exchange in 4 takes place under very mild conditions was expected on the grounds of earlier observations. The temperatures at which [M(q -arene)(CO),] complexes undergo uncatalyzed arene-exchange reactions is 140-160" for M=Cr [50] [26] and 60-80" for M=Mo [50]. Exchange between [Cr(CO),(q6-naphthalene)] and free arene is much more facile [3c] [9b] than in [Cr(benzene)(CO),], and, by extrapolation, must be rapid at ambient temperature in [Mo(CO),(q6-naphthalene)].…”

Section: )mentioning

confidence: 99%

Synthesis and reactivity of naphthalene sandwich complexes of molybdenum. X‐ray structure of [Mo(η⁶‐naphthalene) {P(OMe)₃}₃] and [Mo(H)(η⁶‐naphthalene){P(OMe)₃}₃][BF₄]

Thi

Spichiger

Paglia

et al. 1992

Helvetica Chimica Acta

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The sandwich complexes bis(η6-naphthalene)molybdenum(0) (1), bis(η6-1-methylnaphthalene)molybdenum(0) (2), and bis(η6-1,4-dimethylnaphthalene)molybdenum(0) (3) are synthesized by cocondensation of Mo-atoms with the naphthalene ligands. Complexes 1-3 are also obtained by reduction of MoCl5 or MoCl4. 2THF with highly activated Mg in the presence of the naphthalene ligands. Mg was activated by sublimation of the metal in a simple rotating solution reactor. Complex 2 exists as a mixture of regio- and stereoisomers. Three regioisomers, 3a-c, are formed in reactions of Mo-atoms with 1,4-dimethylnaphthalene, whereas 3a, the isomer with the Mo-atom coordinated to the unsubstituted rings, is formed selectively via the reductive method. The ligands in 1-3 are highly labile. CO displaces both naphthalene rings in 2 and 3 to give [Mo(CO)6], while PF3, P(OMe)3, and PMe3 displace only one coordinated naphthalene in 1 to yield the [Mo(η6-naphthalene)L3] complexes 4-6. In toluene, arene exchange is a competitive process in reactions of 1 with PF3. Complexes 5 (L = P(OMe)3) and 6 (L = PMe3) react with HBF4 to give the cationic metal hydride complexes 8 and 9. The X-ray crystal structures of [Mo(η6-naphthalene) {P(OMe)3}3] (5) and [Mo(H)(η6-naphthalene) {P(OMe)3}3][BF4] (8) are reported

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“…Their (arene)ruthenium() counterparts catalyze enantioselective hydrogen transfer to ketones [7,8] and imines [9] in the presence of enantiomerically pure chiral β-amino alcohols [7] or 1,2-diamines, [8,9] affording high yields and high ees at the same time. Thanks to the particular stability of the areneϪmetal bond, [10] (arene)ruthenium complexes may be converted from Ru 0 into Ru II without the loss of the arene ligand, simply by addition of hydrochloric acid.[2] Only the co-ligands that complete the coordination sphere are exchanged in parallel with the redox process. Of course, it would be very promising to perform the catalytic reactions of (arene)ruthenium complexes in both redox states with enantiopure species whose chirality was connected with the arene ligand.…”

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confidence: 99%

Halogen Atoms as Reactive Centers for the Introduction of Functional Side Chains into (Arene)ruthenium(0) Complexes

et al. 2002

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Substitution of the naphthalene ligand of [(COD)(η 6 -naphthalene)Ru] (2) (COD = 1,5-cyclooctadiene) by suitable haloarenes (halogen = F, Cl, Br, I) affords several new monoand dihaloarene(cyclooctadiene)ruthenium complexes. Depending on the number and position of the halogen and organyl substituents, the haloarenes form achiral or planarchiral π-ligands; [(η 6 -bromoarene)(COD)Ru] complexes are prone to rapid bromine/lithium exchange with nBuLi at low temperatures, while the chloro and fluoro derivatives undergo ortho-metalation under the same conditions. The lithiated species react readily with chiral or achiral electrophiles such as chlorodiorganophosphanes, carbonyl chlorides, aldehydes, lactones, ketones, and epoxides to yield subIntroduction (Arene)ruthenium(0) complexes are useful catalysts for hydrogenation, [2,3] isomerization, [4] and dimerization [5,6] reactions of alkenes. Their (arene)ruthenium() counterparts catalyze enantioselective hydrogen transfer to ketones [7,8] and imines [9] in the presence of enantiomerically pure chiral β-amino alcohols [7] or 1,2-diamines, [8,9] affording high yields and high ees at the same time. Thanks to the particular stability of the areneϪmetal bond, [10] (arene)ruthenium complexes may be converted from Ru 0 into Ru II without the loss of the arene ligand, simply by addition of hydrochloric acid.[2] Only the co-ligands that complete the coordination sphere are exchanged in parallel with the redox process. Of course, it would be very promising to perform the catalytic reactions of (arene)ruthenium complexes in both redox states with enantiopure species whose chirality was connected with the arene ligand. The preparation of [(η 6 -arene)-(COD)Ru] complexes is well known since the work of Bennett, Vitulli, and Pertici, [3,11,12] [13] The lithiated species can be treated with alkyl chloroformates to form ester-substituted [(η 6 -arene)(COD)Ru] compounds. Through the introduction of chiral alkyl chloroformates [alkyl ϭ (Ϫ)-menthyl], this directly affords enantiopure asymmetric complexes. To develop the high potential of this approach, we investigated the preparation and reactivity of (mono-and dihaloarene)ruthenium() complexes systematically. These allow the introduction of many electrophiles of choice. Examples are provided for chlorodiorganophosphanes, carbonyl chlorides, aldehydes, lactones, ketones, and epoxides. Novel (arene)ruthenium() complexes with donor functions such as PR 2 and OH in the side chain are of interest, as these functions should offer the potential to control the reactivity of the different types of (arene)ruthenium catalysts. Results and Discussion Preparation of [(COD)(η 6 -haloarene)Ru] ComplexesMono-or dihaloarenes (fluorobenzene, 1,3-difluorobenzene, 3-fluorotoluene, 3-chlorotoluene, 1,4-dichlorobenzene, 2-bromo-1,4-xylene, 1,3-dibromobenzene, 1-bromo-4-fluorobenzene, 1-bromo-4-iodobenzene, and 4,4Ј-difluoro-1,1Ј-biphenyl) replace the naphthalene ligand of [(COD)(η 6 -naphthalene)Ru] (2) in the presence of acetonitrile at room temperatur...

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Arene transition metal chemistry

Cited by 108 publications

References 46 publications

[Pb₅{Mo(CO)₃}₂]⁴⁻: A Complex Containing a Planar Pb₅ Unit

[Pb₅{Mo(CO)₃}₂]⁴⁻: A Complex Containing a Planar Pb₅ Unit

Synthesis and reactivity of naphthalene sandwich complexes of molybdenum. X‐ray structure of [Mo(η⁶‐naphthalene) {P(OMe)₃}₃] and [Mo(H)(η⁶‐naphthalene){P(OMe)₃}₃][BF₄]

Halogen Atoms as Reactive Centers for the Introduction of Functional Side Chains into (Arene)ruthenium(0) Complexes

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Arene transition metal chemistry

Cited by 108 publications

References 46 publications

[Pb5{Mo(CO)3}2]4−: A Complex Containing a Planar Pb5 Unit

[Pb5{Mo(CO)3}2]4−: A Complex Containing a Planar Pb5 Unit

Synthesis and reactivity of naphthalene sandwich complexes of molybdenum. X‐ray structure of [Mo(η6‐naphthalene) {P(OMe)3}3] and [Mo(H)(η6‐naphthalene){P(OMe)3}3][BF4]

Halogen Atoms as Reactive Centers for the Introduction of Functional Side Chains into (Arene)ruthenium(0) Complexes

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[Pb₅{Mo(CO)₃}₂]⁴⁻: A Complex Containing a Planar Pb₅ Unit

[Pb₅{Mo(CO)₃}₂]⁴⁻: A Complex Containing a Planar Pb₅ Unit

Synthesis and reactivity of naphthalene sandwich complexes of molybdenum. X‐ray structure of [Mo(η⁶‐naphthalene) {P(OMe)₃}₃] and [Mo(H)(η⁶‐naphthalene){P(OMe)₃}₃][BF₄]