Chemistry of cyclopentadienylruthenium and -osmium complexes. 3. New high-yield syntheses of ruthenocenes and osmocenes. The crystal and molecular structures of decamethylruthenocene and decamethylosmocene

Albers, Michel O.; Liles, David C.; Robinson, David J.; Shaver, Alan; Singleton, Eric; Wiege, Manfred; Boeyens, Jan C. A.; Levendis, Demetrius C.

doi:10.1021/om00142a025

Cited by 77 publications

(51 citation statements)

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“…They were characterised by analytical and spectroscopic methods. The phosphorus resonates at low field in Ru 1؊3 (δ ഠ 88 ppm); the same signal appears at higher field in Ru 4 and Ru 5 (δ ഠ 52 ppm). In the free ligands, the phosphorus shows two signals in the 31 P NMR spectrum due to the two regioisomers at about…”

Section: Synthesis Of the Ruthenium Complexesmentioning

confidence: 88%

“…The large downfield shift upon coordination is characteristic of the formation of a five-membered chelate ring. [25] In the 1 H NMR spectra, the signals of the CϪH hydrogen of the linker are low-field shifted in Ru 1؊3 (δ ϭ 4.66, 4.19, and 5.42 ppm respectively); for comparison, the hydrogen resonates at δ ϭ 1.94 and 2.55 ppm for Ru 4 and Ru 5 respectively. The coordinated acetonitrile ligands give rise to two doublets with a long range coupling ( 5 J) with phosphorus of about 1 Hz.…”

Section: Synthesis Of the Ruthenium Complexesmentioning

confidence: 99%

“…Coordinatively unsaturated complexes and complexes with labile ligands are the most promising candidates for catalytic applications, since the availability of a vacant coordination site is a prerequisite for both stoichiometric and catalytic organic transformations at the transition metal centre. Therefore, more labile systems, including [Ru(Cp)(CH 3 CN) 3 ] ϩ , [3] and [Ru(Cp)Cl(COD)], [4] have been developed. In particular, the cationic complex [Ru(Cp) (CH 3 CN) 3 ] ϩ is a promising versatile intermediate since the acetonitrile ligands (AN) are substitutionally labile and can be replaced by other ligands.…”

Section: Introductionmentioning

confidence: 99%

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A New Route to Cationic Half‐Sandwich Ruthenium(II) Complexes with Chiral Cyclopentadienylphosphane Ligands

Doppiu

Salzer

2004

Eur J Inorg Chem

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Section: Synthesis Of the Ruthenium Complexesmentioning

confidence: 88%

Section: Synthesis Of the Ruthenium Complexesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A New Route to Cationic Half‐Sandwich Ruthenium(II) Complexes with Chiral Cyclopentadienylphosphane Ligands

Doppiu

Salzer

2004

Eur J Inorg Chem

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“…Crystal data and parameters of structure solution and refinement are compiled in Table I. The lattice constants and fractional coordinates (Table II) are very similar to those determined for decamethylruthenocene [5].…”

Section: Synthesismentioning

confidence: 63%

Crystal structure of twinned (η5-C5(CH3)4CF3) (η5-C5(CH3)5)Ru

1994

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The substituted sandwich complex crystallizes in monoclinic space group P21/m with Z = 2. Twinning to the (001) direction with the special condition c*/4a* = cos /5* causes systematic superposition of the reciprocal lattices of both domains and results in an apparent unit cell with double volume and the reflection condition (2h)kl, l = 2n. The structure solution was obtained with the subset of intensity data for the predominant individuum and converged at R = 0.040, Rw ---0.046 for 832 independent observations and 122 variables. The molecules show disorder with respect to the crystallographic mirror plane. The structure is closely related to that of deeamethylruthenocene.

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“…D 5h -Symmetrie (M = Ru [14,15], Os [15]) auf Grund unserer Raman-spektroskopischen Polarisationsmessungen orientierter Einkristalle und der Ergebnisse begleitender DFT-Rechnungen revidiert werden [9, 16 -18]. DieÜbereinstimmungen zwischen den Ergebnissen der Polarisationsexperimente und der DFT-Rechnungen waren dabei jeweils exzellent [9, 16 -18] (z.…”

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Zur Elektronenstruktur metallorganischer Komplexe der ƒ -Elemente, 81. Berechnung der Normalschwingungen von La(η⁵-C₅H₅)₃(NCCH₃)₂ auf der Basis der Dichtefunktionaltheorie sowie vibronische Kopplungen und Auffindung weiterer rein elektronischer Absorptions- und Lumineszenzüberg¨ange bei [La(η⁵-C₅H₅)₃(NCCH₃)₂:Nd³⁺] / Electronic Structures of Organometallic Complexe

Amberger

Reddmann

2013

Zeitschrift Für Naturforschung B

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The planned model calculations of normal modes of pseudo-trigonal-bipyramidal LaCp 3 (NCCH 3 ) 2 (Cp = η 5 -C 5 H 5 − ) (1) adopting density functional theory (DFT), and using the molecular structure as suggested by X-ray investigations, did not converge. Alternatively, DFT calculations assuming molecular C 3h symmetry were performed. Unfortunately, these calculations did not reproduce the experimentally derived frequencies of the skeletal modes very well, including a wrong energetic sequence of the four previously unambiguously assigned (close lying) Raman-active ν(La-Cp) skeletal modes. The same presumably also holds for DFT calculations made for LaCp 3 ·NCCH 3 (2) and base-free LaCp 3 (3), assuming molecular C 3 and C 3h symmetry, respectively. In order to check whether the calculated incorrect sequence is produced by the five-membered Cp rings, a DFT calculation also has been performed for the hypothetical model complex [La(η 6 -C 6 H 6 ) 3 ] 3+ (4) of D 3 symmetry.A closer examination of the vibronic sidebands of the hypersensitive absorption transition 4 I 9/2 → 4 G 5/2 of [LaCp 3 (NCCH 3 ) 2 :Nd 3+ ] (5) showed that first of all, totally symmetric intraligand and not skeletal vibrations are coupling as it was the case for [LaCp 3 (NCCH 3 ) 2 :Ln 3+ ] (Ln = Pr, Sm). Applying this result to the vibronic sidebands of some purely electronic crystal field (CF) transitions, which are hampered by strong binary combination vibrations, the energies of these CF levels could be determined. The CF state 1Γ 8 of the ground multiplet 4 I 9/2 of [LaCp 3 (NCCH 3 ) 2 :Nd 3+ ], which previously could not be detected by absorption measurements, could be derived from the luminescence transition 4 F 3/2 → 4 I 9/2 . Considering these additional assignments, the goodness of the fit increased from 32.3 to 29.9 cm −1 for 61 assignments.

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Chemistry of cyclopentadienylruthenium and -osmium complexes. 3. New high-yield syntheses of ruthenocenes and osmocenes. The crystal and molecular structures of decamethylruthenocene and decamethylosmocene

Cited by 77 publications

References 4 publications

A New Route to Cationic Half‐Sandwich Ruthenium(II) Complexes with Chiral Cyclopentadienylphosphane Ligands

A New Route to Cationic Half‐Sandwich Ruthenium(II) Complexes with Chiral Cyclopentadienylphosphane Ligands

Crystal structure of twinned (η5-C5(CH3)4CF3) (η5-C5(CH3)5)Ru

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