Chemistry of the Cyciopentadienyl Bisphosphine Ruthenium Auxiliary

Davies, Stephen G.; McNally, John P.; Smallridge, Andrew J.

doi:10.1016/s0065-3055(08)60498-0

Cited by 195 publications

(137 citation statements)

References 108 publications

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“…Alternatively, the triphenylphosphine ligand in 1 can be replaced by carrying out the substitution reactions in benzene. This reactivity is similar to that of the well-known RuCl(PPh,),(Cp) complex (Cp = T5-cyclopentadienyl), which also contains a facial six-electron donor ligand (4). Our interest in 2-pyridylphosphine complexes stems from their potential as homogeneous catalysts in aqueous media (5).…”

Section: Introductionsupporting

confidence: 56%

“…The resulting turbid, orange solution was filtered through Celite 545@ along with acetone washings (15 mL 4 To a suspension of 1 (0.085 g, 0.121 mmol) and NH,PF, (0.020 g, 0.122 mmol) in MeOH (4 mL) was added a solution of MeCN in MeOH (1 mL, made by mixing 0.05 mL of MeCN in 5 mL of MeOH) and the resulting mixture refluxed for 10 min. The orange solution was pumped to dryness and the residue dissolved in acetone (5 mL) and filtered through Celite 545@.…”

Section: Preparation Of [Ruc~(co)(pp~)(p~~~)]pf~~mentioning

confidence: 99%

“…By use of a nonpolar solvent such as benzene, the PPh, in 1 is readily displaced, the chemistry being similar to that of RuCl(PPh,),(Cp), where the PPh, has been replaced by other phosphines, CO, and isocyanides, to name a few (4).…”

Section: Triphenylphosphine-substitution Reactionsmentioning

confidence: 99%

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Synthesis, characterization, and reactivity of a ruthenium(II)N,N′,N″-tris(2-pyridyl)phosphine complex. X-ray analysis of RuCl₂(PPh₃)(Ppy₃) (py = 2-pyridyl)

Schutte¹,

Rettig²,

James³

1996

Can. J. Chem.

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Section: Introductionsupporting

confidence: 56%

Section: Preparation Of [Ruc~(co)(pp~)(p~~~)]pf~~mentioning

confidence: 99%

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Synthesis, characterization, and reactivity of a ruthenium(II)N,N′,N″-tris(2-pyridyl)phosphine complex. X-ray analysis of RuCl₂(PPh₃)(Ppy₃) (py = 2-pyridyl)

Schutte¹,

Rettig²,

James³

1996

Can. J. Chem.

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“…A large number of bis(phosphine)(r/5-C5Hs)Ru n halide complexes have been prepared and the structures of (~75-CsHs)RuC1L2 (L = PMe3, PPh3) have been described (Bruce, Wong, Skelton & White, 1981). The ancillary chloride and phosphine ligands in these complexes can be readily replaced to give a variety of neutral and cationic derivatives, including (r/5-Cp)Ru n complexes containing chelating phosphines (Davies, McNally & Smallridge, 1990). The preparations of two complexes containing the chelating phosphines 1,2-bis(cyclohexylphosphino)methane (dcpm) and 2-methyl-1,2-bis(triphenylphosphino)ethane (prophos) have recently been described and their structures determined (Joslin, Mague & Roundhill, 1991;Morandini, Consiglio, Straub, Ciani & Sironi, 1983).…”

Section: Commentmentioning

confidence: 99%

Structure of [1,2-bis(diphenylphosphino)ethane]chloro(η5-cyclopentadienyl)ruthenium(II)

Suravajjala¹,

Porter²

1993

Acta Crystallogr C

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The asymmetric unit is comprised of a molecule of (r/5-Cp)RuCl(dppe), where dppe is 1,2-bis(diphenylphosphino)ethane, and a co-crystallized molecule of dppe group, a chloride ligand and the cyclopentadienyl ligand. The bond to Cl(1) measures 2.452 (2)/~ and bonds to the P atoms measure 2.275 (2) and 2.282 (2) A for Ru(1)--P(1) and Ru(1)--P(2), respectively.Within the cyclopentadienyl ligand we find the five C atoms to be essentially coplanar with a maximum out-of-plane displacement of 0.0123 A (mean deviation of 0.0079 A) and C---C bonds in the range 1.372 (8) to 1.421 (9)•. The Ru atom is 1.851/~ Acta Crystallographica Section C ISSN 0108-2701 ©1993REGULAR STRUCTURAL PAPERS 1457 from the centroid defined by the five C atoms of the Cp ring and is displaced slightly (approximately 0.08 A) towards the C(54) and C(55) atoms which are trans to Cl(1). Structural features of this complex resemble the chiral complex (r/5-Cp)RuCl(prophos), where prophos is a chiral derivative of dppe containing a methyl group on the ethylene bridge (Morandini, Consiglio, Straub, Ciani & Sironi, 1983). Bond lengths and angles within the coordination sphere of the Ru atom are also in good agreement with those reported for another (r/5-Cp)Ru n chloride complex containing dcpm. A principal difference between the two lies in the bite angle of the latter which, owing to the fact that it contains one atom less in the carbon bridge linking the two phosphine moieties, is remarkably acute [P--Ru--P= 69.57 (8) ° (Joslin, Mague & Roundhill, 1991)].Significantly, the nature of the ancillary R group bonded to P of the phosphine ligand appears to have only a minor influence on the coordination geometry about the transition-metal center. A comparison of the structures of complexes containing chelating phosphines with those containing monodentate phosphines such as ('r/5-Cp)RuCI(PR3)2 (R = Ph, Me) indicates that the P--Ru--P angle in those complexes containing chelating phosphines is acute, whereas in complexes containing either PMe3 or PPh3 the P--Ru--P angles are obtuse (Bruce, Wong, Skelton & White, 1981). C (2) C (3) .... C(15) CI(ll C1321 REGULAR STRUCTURAL PAPERSC(42) 0.4199 0.6288 0.9674 0.061 (2) C(43) 0.4296 0.7406 0.9353 0.061 (2Phenyl rings were refined as rigid groups using H atoms placed in idealized postious with fixed isotropic U = 0.08 .~2. The Tll reflection suffered from extinction and was therefore omitted during the refinement process. All structure calculations were performed with the SHELXTL-Plus system (Sheldrick, 1990).Acknowledgement is made to the Donors of the Petroleum Research Fund, administered by the American Chemical Society, for partial support of this research, and also to the Welch Foundation. We wish to thank especiaUy the Engelhard Corporation for their gift of ruthenium trichloride, and F. Cervantes-Lee for collecting the intensity data. AbstractThe tetranuclear ruthenium carbonyl hydride cluster, di-/z-carbonyl-undecacarbonyl-di#z-hydrido-tetrahedro-tetraruthenium(6Ru--Ru), crystallizes in a monoclini...

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“…[153] Ein häufig angewendeter Syntheseweg beruht auf der Umsetzung des Ru-Halogenids (meist des Chlorids) mit einem terminalen Alkinylliganden unter Bildung des Vinylidenkations, das zwar isoliert werden kann, oft aber in situ mit Methoxid zur Bildung der s-Alkinylprodukte in guten Ausbeuten deprotoniert wird (Schema 37). [154][155][156] Die Komplexe sind hauptsächlich wegen ihrer potenziellen nichtlinearen optischen Eigenschaften ins Blickfeld gerückt, nachdem gezeigt worden war, dass die Elektronendonoreigenschaften der Rutheniumeinheit die molekulare Hyperpolarisierbarkeit zweiter Ordnung begünstigt.…”

Section: Cyclopentadienyl-und Arenruthenium(ii)-alkinyleunclassified

Metall‐Alkinyl‐σ‐Komplexe: Synthesen und Materialien

Long

Williams

2003

Angewandte Chemie

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Metallalkinylkomplexe bergen eine große Anziehungskraft für die Synthesechemie, die Strukturchemie und die Materialwissenschaften, sodass mittlerweile eine Vielzahl von Reaktionen zur M‐CC‐Verknüpfung mit einer ganzen Skala von Übergangsmetall‐ und Alkinylreagentien entwickelt wurde. Einige Methoden sind breit anwendbar, andere beschränken sich auf ein spezielles Metall oder Substrat. Wegen der linearen Geometrie der Alkinyleinheit und ihrem ungesättigten Charakter sind die Metallalkinyle attraktive Bausteine für molekulare Drähte und polymere metallorganische Materialien, die interessante physikalische Eigenschaften wie flüssigkristallines Verhalten, optische Nichtlinearität, Lumineszenz und elektrische Leitfähigkeit aufweisen können. Dieses einzigartige Spektrum an Eigenschaften steht als treibende Kraft hinter der intensiven Erforschung von Metall‐Alkinyl‐σ‐Komplexen. Die Entwicklung und Fortschritte insbesondere der letzten zehn Jahre werden in diesem Aufsatz zusammengefasst.

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Chemistry of the Cyciopentadienyl Bisphosphine Ruthenium Auxiliary

Cited by 195 publications

References 108 publications

Synthesis, characterization, and reactivity of a ruthenium(II)N,N′,N″-tris(2-pyridyl)phosphine complex. X-ray analysis of RuCl₂(PPh₃)(Ppy₃) (py = 2-pyridyl)

Synthesis, characterization, and reactivity of a ruthenium(II)N,N′,N″-tris(2-pyridyl)phosphine complex. X-ray analysis of RuCl₂(PPh₃)(Ppy₃) (py = 2-pyridyl)

Structure of [1,2-bis(diphenylphosphino)ethane]chloro(η5-cyclopentadienyl)ruthenium(II)

Metall‐Alkinyl‐σ‐Komplexe: Synthesen und Materialien

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Chemistry of the Cyciopentadienyl Bisphosphine Ruthenium Auxiliary

Cited by 195 publications

References 108 publications

Synthesis, characterization, and reactivity of a ruthenium(II)N,N′,N″-tris(2-pyridyl)phosphine complex. X-ray analysis of RuCl2(PPh3)(Ppy3) (py = 2-pyridyl)

Synthesis, characterization, and reactivity of a ruthenium(II)N,N′,N″-tris(2-pyridyl)phosphine complex. X-ray analysis of RuCl2(PPh3)(Ppy3) (py = 2-pyridyl)

Structure of [1,2-bis(diphenylphosphino)ethane]chloro(η5-cyclopentadienyl)ruthenium(II)

Metall‐Alkinyl‐σ‐Komplexe: Synthesen und Materialien

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Synthesis, characterization, and reactivity of a ruthenium(II)N,N′,N″-tris(2-pyridyl)phosphine complex. X-ray analysis of RuCl₂(PPh₃)(Ppy₃) (py = 2-pyridyl)

Synthesis, characterization, and reactivity of a ruthenium(II)N,N′,N″-tris(2-pyridyl)phosphine complex. X-ray analysis of RuCl₂(PPh₃)(Ppy₃) (py = 2-pyridyl)