1998
DOI: 10.1021/om9801195
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Activation of η5-Cyclopentadienyl Ligands toward Nucleophilic Attack through η5 → η3 Ring Slippage. Kinetics, Thermodynamics, and NMR Spectroscopy

Abstract: The kinetics of the reactions of the complexes [Ru(η5-C5H5)(η4-C5H4O)(L)]CF3SO3 (L = CH3CN, pyridine, thiourea) with PMe3 have been studied in acetone. The novel reaction products [Ru(η3-C5H5)(η4-C5H4O)(PMe3)(L)]CF3SO3 formed are fluxional in solution due to an intramolecular enantiomeric equilibrium likely proceeding through a five-coordinate η1-C5H5 intermediate.

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Cited by 30 publications
(12 citation statements)
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“…The same conclusion is drawn from 13 C{ 1 H} NMR spectroscopy. This has been demonstrated previously for 8a . The dynamic behavior of complexes 6 − 8 has been rationalized by an intramolecular enantiomeric equilibrium leading to an inversion of ruthenium as shown in Scheme .…”
Section: Resultssupporting
confidence: 68%
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“…The same conclusion is drawn from 13 C{ 1 H} NMR spectroscopy. This has been demonstrated previously for 8a . The dynamic behavior of complexes 6 − 8 has been rationalized by an intramolecular enantiomeric equilibrium leading to an inversion of ruthenium as shown in Scheme .…”
Section: Resultssupporting
confidence: 68%
“…For the ligands, nonconjugated and conjugated olefins are among the most reactive substrates, while aromatic ligands, in particular the cyclopentadienyl anion, are among the least reactive . It was thus a surprise to find that tertiary phosphines react with the cationic 18-electron complexes [Ru(η 5 -C 5 H 5 )(η 4 -C 5 H 4 O)] 2 2+ ( 1 ) and [Ru(η 5 -C 5 H 5 )(η 4 -C 5 H 4 O)(L)] + (L = CH 3 CN ( 2 ), pyridine ( 3 ), thiourea ( 4 )) to give 1,1‘-disubstituted ruthenocenes [Ru(η 5 -C 5 H 4 PR 3 )(η 5 -C 5 H 4 OH)] + ( 12 ) (paths i and ii, Scheme ) as well as the anticipated 1,2-disubstituted ruthenocenes ( 13 ), formed via η 3 -cyclopentenoyl complexes [Ru(η 5 -C 5 H 5 )(η 3 -C 5 H 4 O−PR 3 )(L)] + (path iii, Scheme ). , Scheme gives an overview of the reactions hitherto analyzed on a synthetic level. Thus, 1 yields only 12 irrespective of the nature of the phosphine, whereas complexes 2 − 4 give 13 as well.…”
Section: Introductionmentioning
confidence: 99%
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“…[17] Phenyl groups on the cyclopentadienyl are known to favor h 5 to h 3 ring slip since they stabilize the h 3 intermediate by conjugation with the aromatic rings. [18] Furthermore, Kirchner et al have characterized h 3 -cyclopentadienylruthenium complexes by NMR spectroscopy, [19] which were formed by reaction of h…”
Section: Wwwchemeurjorgmentioning
confidence: 99%
“…A large number of ligands has been tested, as a survey of the Cambridge Structural Database (CSD) [17] shows. There are structurally characterized complexes with h 3 -coordinated Cp, in solution [18] and in the solid state, [19,20] as well as ligands with larger p systems, such as fluorenyl (C 13 H 9 À ), cyclopentha[def]phenantrenyl (C 15 H 9 À ), [21±28] and 1-hydronaphthalene (C 10 H 9 À ); [29,30] however, the most studied ligand is certainly indenyl. [21, 31±56] Since the early papers by the Hoffmann group [2,57,58] a large amount of work has been devoted to the theoretical understanding of haptotropic shifts.…”
Section: Introductionmentioning
confidence: 99%