Chemistry of the metal carbonyls. Part LIII. Some dicarbonyl-(π-cyclopentadienyl)ruthenium complexes containing metal–metal bonds

Blackmore, T.; Cotton, John D.; Bruce, Michael I.; Stone, F. G. A.

doi:10.1039/j19680002931

Cited by 76 publications

(21 citation statements)

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“…As depicted in Figure S2, this is particularly true for the broad bands centered at 1815 and 1536/1468 cm -1 and hence it can be concluded that CO ligands are present in the black solid. Carbonyl stretching frequencies as low as 1612 cm -1 have been reported before for ruthenium clusters 7 and in some anionic osmium carbonyl complexes ion pairing effects between CO molecules and K + have been identified as a reason for low CO stretching frequencies (1625 cm -1 ). 8 Similar effects may also be operative in the present case.…”

Section: Atr Ir Spectroscopy and 13 Co Labelingmentioning

confidence: 97%

Revisiting the Synthesis and Elucidating the Structure of Potassium Cyclopentadienyldicarbonylruthenate, K[CpRu(CO)₂]

et al. 2014

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Known procedures for the synthesis of K[CpRu(CO)2] (KRp) via reductive cleavage of the ruthenium dimer Rp2 were found to be inconsistent and have thus been revisited, and a revised protocol using K[HB(sec-Bu)3] (K-Selectride) as the reducing agent is now reported that gives yellow KRp in crystalline form in around 40% yield. The structure of KRp·THF has been determined by X-ray diffraction, representing the first crystallographic characterization of an Rp– salt. Inevitably the reductive cleavage of Rp2 also gives a poorly soluble black solid as an additional product, which has now been analyzed by a variety of methods, including 13C MAS NMR spectroscopy using 13CO-labeled material. The black solid has been identified as a polymeric Cp/Ru/CO compound with both bridging and terminal CO ligands in a 3:1 ratio. The present report may stimulate the use of the [CpRu(CO)2]− (Rp–) anion, which has been barely exploited as yet in comparison to its popular congener [CpFe(CO)2]− (Fp–).

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Section: Atr Ir Spectroscopy and 13 Co Labelingmentioning

confidence: 97%

Revisiting the Synthesis and Elucidating the Structure of Potassium Cyclopentadienyldicarbonylruthenate, K[CpRu(CO)₂]

et al. 2014

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“…(n = 1: L = CH3CN, Propen, Cyclohexen; wurden im übrigen schon früher auf ähnliche Weise erhalten [9,10].…”

Section: Präparative Ergebnisse A) [Rls-cbhbru(co)il]+ Und {[^-Cbhbruunclassified

“…5 wurden im übrigen schon früher auf ähnliche Weise erhalten [9,10].Der Reaktions verlauf läßt sich am besten durch die intermediäre Bildung von ); 5 -C5H5RU(CO)2C1... A1C13 erklären, wobei der Ligand L die entstehende Koordinationslücke besetzt [11]. Gestützt wird diese Deutung auch durch die experimentelle Erfahrung, daß ^5-C5H5RU(CO)2C1 mit CH3CN oder Olefinen in Abwesenheit von AICI3 nicht reagiert.…”

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neuer substituierter ƞ⁵ -Cyclopentadienyl-ruthenium-carbonyl-Kationen / Syntheses and Spectral Data of New Substituted ƞ⁵ -Cyclopentadienyl Ruthenium Carbonyl Cations

Jungbauer

Behrens

1978

Zeitschrift Für Naturforschung B

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“…It has been proposed that a more electron-rich metal, such as Ru, may enhance the backbonding properties over those in the analogous Fe alkynyls [44,45] The same trend is apparent for a pair of metal alkynyls also listed in molecules reveals a difference of only 4 cm -1 (Fe = 2104 cm -1 ; Ru = 2108 cm -1 ), again highlighting the limitations of the ligand stretching frequencies in characterizing electronic structure and bonding properties [62].…”

Section: Trends From Fe To Rumentioning

confidence: 79%

Experimental measure of metal–alkynyl electronic structure interactions by photoelectron spectroscopy: (η5-C5H5)Ru(CO)2C CMe and [(η5-C5H5)Ru(CO)2]2(μ-C C)

et al. 2015

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The gas-phase He I and He II photoelectron spectra of the propynylruthenium molecule CpRu(CO) 2 C≡CMe (Cp = η 5-C 5 H 5) and the ethynediyldiruthenium molecule [CpRu(CO) 2 ] 2 (µ-C≡C) are compared with the spectrum of CpRu(CO) 2 Cl to experimentally determine electronic structure interactions of the alkynyl ligands with the metal. The spectra indicate that the interaction between the filled metal-dπ and filled alkynyl-π orbitals dominates the metal-alkynyl π electronic structure, mirroring previously characterized CpFe(CO) 2 alkynyls. All valence ionizations of the Ru molecules are stabilized with respect to similar Fe compounds, contrary to the common expectation of lower ionization energies with atomic substitution down a column of the periodic table. Ab initio electronic structure calculations suggest that this stabilization traces to the greater inherent electronic relaxation energy associated with removal of Fe 3d electrons compared to removal of Ru 4d electrons. Destabilization of the first two ionization bands of the diruthenium molecule are a result of filled-filled interactions between alkynyl π-bonds with the symmetric combination of metal-metal-dπ orbitals, showing electronic communication between the metals through the alkynyl bridge. From the photoelectron spectrum, this communication was calculated to have a minimum electron-transfer integral of 0.56 eV. The stabilization of the antisymmetric combination of the metal-metal-dπ orbitals gives a direct and unique experimental measure of the interaction with the alkynyl π* orbitals. The stabilization caused by the alkynyl π* orbitals was found to be approximately one-third of the destabilization caused by the filled-filled interaction with the alkynyl π-bonds and about one-fourth to one-third the stabilization provided by back-bonding to a carbonyl ligand.

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Chemistry of the metal carbonyls. Part LIII. Some dicarbonyl-(π-cyclopentadienyl)ruthenium complexes containing metal–metal bonds

Cited by 76 publications

References 0 publications

Revisiting the Synthesis and Elucidating the Structure of Potassium Cyclopentadienyldicarbonylruthenate, K[CpRu(CO)₂]

Revisiting the Synthesis and Elucidating the Structure of Potassium Cyclopentadienyldicarbonylruthenate, K[CpRu(CO)₂]

neuer substituierter ƞ⁵ -Cyclopentadienyl-ruthenium-carbonyl-Kationen / Syntheses and Spectral Data of New Substituted ƞ⁵ -Cyclopentadienyl Ruthenium Carbonyl Cations

Experimental measure of metal–alkynyl electronic structure interactions by photoelectron spectroscopy: (η5-C5H5)Ru(CO)2C CMe and [(η5-C5H5)Ru(CO)2]2(μ-C C)

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Chemistry of the metal carbonyls. Part LIII. Some dicarbonyl-(π-cyclopentadienyl)ruthenium complexes containing metal–metal bonds

Cited by 76 publications

References 0 publications

Revisiting the Synthesis and Elucidating the Structure of Potassium Cyclopentadienyldicarbonylruthenate, K[CpRu(CO)2]

Revisiting the Synthesis and Elucidating the Structure of Potassium Cyclopentadienyldicarbonylruthenate, K[CpRu(CO)2]

neuer substituierter ƞ5 -Cyclopentadienyl-ruthenium-carbonyl-Kationen / Syntheses and Spectral Data of New Substituted ƞ5 -Cyclopentadienyl Ruthenium Carbonyl Cations

Experimental measure of metal–alkynyl electronic structure interactions by photoelectron spectroscopy: (η5-C5H5)Ru(CO)2C CMe and [(η5-C5H5)Ru(CO)2]2(μ-C C)

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Revisiting the Synthesis and Elucidating the Structure of Potassium Cyclopentadienyldicarbonylruthenate, K[CpRu(CO)₂]

Revisiting the Synthesis and Elucidating the Structure of Potassium Cyclopentadienyldicarbonylruthenate, K[CpRu(CO)₂]

neuer substituierter ƞ⁵ -Cyclopentadienyl-ruthenium-carbonyl-Kationen / Syntheses and Spectral Data of New Substituted ƞ⁵ -Cyclopentadienyl Ruthenium Carbonyl Cations