Second sphere coordination behavior of aquo and amine ligands bound to a η6-benzeneruthenium(II) cation

Asano, Hideo; Miyaki, Yoshiharu

doi:10.1016/s0020-1693(97)05829-5

Cited by 27 publications

(10 citation statements)

References 24 publications

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“…The structure of the dicationic bis aquo-complex [Ru(Cp*)(η 3 -C 3 H 5 )(H 2 O) 2 ] 2+ , 12 , was determined by X-ray diffraction methods, and a view of the cation is given in Figure , along with a selection of bond lengths and bond angles. Although Ru(H 2 O) complexes are known, − this is the first such structure with camphor sulfonic acid anions and supports the view that this bulky sulfonic acid anion will not be a strong ligand. The immediate coordination sphere contains the Cp*, the η 3 -C 3 H 5 , and two water molecules.…”

Section: Resultssupporting

confidence: 57%

Rapid, Selective Ru-Sulfonate-Catalyzed Allylation of Indoles Using Alcohols as Substrates

et al. 2009

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The Ru-catalyzed allylation of differing indole compounds using ArCH(OH)CHdCH 2 (Ar ) Ph, 2-CH 3 C 6 H 4 , 2-CH 3 OC 6 H 4 2-ClC 6 H 4 , and 1-naphthyl) is relatively fast (usually <30 min for 100% conversion) at ambient temperature in the presence of [Ru(Cp*)(CH 3 CN) 3 ](PF 6 ) + a sulfonic acid cocatalyst, RSO 3 H (R ) p-tolyl, a camphor fragment or CH 3 ). The new catalysts allow allyl alcohols rather than carbonates, halides, acetates, etc., to be used as substrates in this allylation chemistry, thereby avoiding the use of a (wasted) leaving group. The branched products are favored, and in a number of examples b/l ratios in excess of 20 are observed. The catalyst is selective in that there is little or no N-allylation. The use of acids such as CF 3 SO 3 H or HBF 4 results in slower and/or less selective reactions. Although phosphoric acid additives show some promise, carboxylic acids are much less effective or do not catalyze the reaction at all. The preformed isolated complexes [Ru(Cp*)(η 3 -C 3 H 5 )(RSO 3 ) 2 ] are efficient catalyst precursors; however, NMR experiments suggest that one of the active species is the monosulfonate cationic complex [Ru(Cp*)(η 3 -C 3 H 5 )(CH 3 CN)(RSO 3 )] + . Stoichiometric oxidative addition reactions are shown to be relatively rapid. New Ru(Cp*) complexes have been generated and characterized by NMR methods. DFT calculations suggest that the large b/l ratios observed have a structural basis in that the Ru-C(allyl) bond length for the substituted terminal allyl carbon, Ru-C(1), is relatively long. X-ray structures for Ru(Cp*)(η 3 -C 3 H 5 )(SO 4 ) and the dication [Ru(Cp*)(η 3 -C 3 H 5 )(H 2 O) 2 ] 2+ (as a camphor sulfonate salt) are reported.

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Section: Resultssupporting

confidence: 57%

Rapid, Selective Ru-Sulfonate-Catalyzed Allylation of Indoles Using Alcohols as Substrates

et al. 2009

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“…Kurosawa et al. suggested, on the basis of kinetic measurements, that acetone may hydrogen bond to the coordinated water in [Ru(OH 2 )(Ph-bop)(C 6 H 6 )][BF 4 ] 2 ( 13 ) . The observation of separate signals for coordinated H 2 O and HOD shows that proton exchange is slow on the NMR time scale.…”

Section: Resultsmentioning

confidence: 99%

“…In the past decade there has been a surge of interest in chiral nitrogen-donor ligands for use in asymmetric catalysis and bidentate, C 2 -symmetry ligands such as semicorrins and particularly bis(oxazolines) have been very successful. , The use of C 2 -symmetry nitrogen donor ligands in (arene)ruthenium complexes has been studied much less well. Kurosawa et al have studied bis(phenyloxazolinyl)propane complexes, and a diaminobiphenyl complex in which the ligand has axial chirality has also been reported . In this paper we report the synthesis of several (arene)ruthenium complexes with three different types of bis(oxazolines) (N-N), namely bis(2-oxazoline) (box), 2,2-bis(2-oxazolinyl)propane (bop), and 1,2-bis(2-oxazolinyl)benzene (benbox).…”

Section: Introductionmentioning

confidence: 96%

(Arene)ruthenium Complexes with Bis(oxazolines): Synthesis and Applications as Asymmetric Catalysts for Diels−Alder Reactions

et al. 2001

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Reaction of the dimers [RuCl 2 (arene)] 2 (arene ) benzene, p-cymene, mesitylene) with bis-(oxazolines) (N-N ) bis(2-oxazoline) (box), 2,2-bis(2-oxazolinyl)propane (bop), 1,2-bis(2oxazolinyl)benzene (benbox)) in the presence of NaSbF 6 gives the complexes [RuCl(N-N)(arene)][SbF 6 ] (1-8), which have been fully characterized. Treatment of these cations with AgSbF 6 generates dications which in some cases are enantioselective catalysts for Diels-Alder reaction of methacrolein and cyclopentadiene. Two complexes, [RuCl( i Pr-benbox)(pcymene)][SbF 6 ] ( 5) and [Ru(OH 2 )( i Pr-bop)(mes)][SbF 6 ] 2 (10; mes ) mesitylene), have been characterized by X-ray crystallography.

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“…The ruthenium complex has attracted much attention, and five structures (Table , entries 32−36) are reported. Only the complex of ( S )- 1 with the tridentate ligand 2,2‘:6‘,2‘ ‘-terpyridine (Table , entry 32) has an octahedral structure; four other structures, with either ( R )- 1 or ( S )- 3c ligands (Table , entries 33−36) and a variety of anions or additional ligands, all have a tetrahedral structure. − …”

Section: Structures Of Box−metal Complexesmentioning

confidence: 99%

C₂-Symmetric Chiral Bis(Oxazoline) Ligands in Asymmetric Catalysis

2006

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Second sphere coordination behavior of aquo and amine ligands bound to a η6-benzeneruthenium(II) cation

Cited by 27 publications

References 24 publications

Rapid, Selective Ru-Sulfonate-Catalyzed Allylation of Indoles Using Alcohols as Substrates

Rapid, Selective Ru-Sulfonate-Catalyzed Allylation of Indoles Using Alcohols as Substrates

(Arene)ruthenium Complexes with Bis(oxazolines): Synthesis and Applications as Asymmetric Catalysts for Diels−Alder Reactions

C₂-Symmetric Chiral Bis(Oxazoline) Ligands in Asymmetric Catalysis

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Second sphere coordination behavior of aquo and amine ligands bound to a η6-benzeneruthenium(II) cation

Cited by 27 publications

References 24 publications

Rapid, Selective Ru-Sulfonate-Catalyzed Allylation of Indoles Using Alcohols as Substrates

Rapid, Selective Ru-Sulfonate-Catalyzed Allylation of Indoles Using Alcohols as Substrates

(Arene)ruthenium Complexes with Bis(oxazolines): Synthesis and Applications as Asymmetric Catalysts for Diels−Alder Reactions

C2-Symmetric Chiral Bis(Oxazoline) Ligands in Asymmetric Catalysis

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C₂-Symmetric Chiral Bis(Oxazoline) Ligands in Asymmetric Catalysis