(.eta.6-Naphthalene)(.eta.4-1,5-cyclooctadiene)ruthenium(0): efficient synthesis, chemistry, and catalytic properties

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

“…Not only 1,2,4-trimethylbenzene, but also 1,2,3,4-tetramethylbenzene, are prone to this type of reaction. [3] Two of the (dihalobenzene)ruthenium complexes have been characterized by X-ray diffraction: [(η 6 -1-bromo-4-fluorobenzene)(COD)Ru] (10) and [(η 6 -1-bromo-4-iodobenzene)(COD)Ru] (11) (Figure 1). Thanks to the pronounced chemical differences between their halogen atoms, 10 and 11 are both suitable for stepwise substitution reactions.…”

“…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.…”

“…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.…”

Dinuclear π Complexes of Yttrium and Lutetium with Sandwiched Naphthalene and Anthracene Ligands: Evidence for Rapid Intramolecular Inter-Ring Rearrangements

“…[1] In particular, benzene and substituted benzenes coordinated to Cr(CO) 3 have played a central role in this area. Less well developed, but potentially useful, are studies of the coordination of polycyclic arenes such as naphthalene and anthracene to metal atoms.…”

Slipped μ‐Indenyl Triple‐Decker Complexes Containing (C4Me4)Co and (C5R5)Ru Fragments

“…A few µ-naphthalene triple-decker complexes are known: [(η 6 -C 6 H 6 )Cr(µ:η 6 :η 6 -C 10 H 8 )Cr(η 6 -C 6 H 6 )], [5] [(C 5 R 5 )M(µ:η 6 :η 6 -C 10 H 8 )M(C 5 R 5 )] (M = V, Fe [6] ), and [(cod)Ru(µ:η 6 :η 6 -C 10 H 8 )Ru(cod)]. [7] µ-Indenyl derivatives are the least studied, and the first examples, the ruthenium complexes [(C 5 R 5 )Ru(µ:η 5 :η 6 -C 9 H 7 )Ru(C 5 R 5 )] + , [8] were prepared by electrophilic stacking of [(C 5 R 5 )Ru(η 5 -C 9 H 7 )] with [(C 5 R 5 )Ru] + fragments.…”