Bis(<i>η</i><sup>6</sup>‐phosphabenzol)vanadium: Synthese, Redoxeigenschaften, Struktur und konformative Beweglichkeit

Elschenbroich, Christoph; Nowotny, Mathias; Metz, Bernhard; Massa, Werner; Graulich, J.

doi:10.1002/ange.19911030531

Cited by 24 publications

(4 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Eine Serie von homoleptischen Komplexen der Stammverbindung Phosphinin (L) umfasst die Spezies [NiL 4 ], [CrL 6 ] und [FeL 5 ] 232. η 6 ‐Komplexe wie der Sandwich‐Komplex [V(η 6 ‐L) 2 ] sind ebenfalls beschrieben 233. Mit den durch C‐C‐Homokupplung der 2‐Zirconiumderivate zugänglichen 2,2′‐Biphosphininen (BPs)234 lässt sich eine Anzahl von sehr stabilen homoleptischen Chelatkomplexen erhalten: [Ni(BP) 2 ], [M(BP) 3 ] (M=Cr, Mo, W), [M(BP) 3 ] 2− (M=Ti, Zr), [M(BP) 2 ] − (M=Co, Rh), [M(BP) 2 ] 2− (M=Fe, Ru) 235.…”

Section: Besondere Elektronenkonfigurationenunclassified

Phosphaorganische Chemie: Panorama und Perspektiven

Mathey

2003

Angewandte Chemie

198

View full text Add to dashboard Cite

Die gesamte phosphororganische Chemie wurde mit Beginn der siebziger Jahre infolge der Entdeckung stabiler phosphororganischer Derivate mit Koordinationszahlen des Phosphors von 1 oder 2 aufgefrischt. Bezüglich ihrer Chemie gleichen diese Verbindungen ihren reinen Kohlenstoff‐Analoga. Dieser Aufsatz widmet sich der Analogie zwischen den Phosphorderivaten und den entsprechenden Alkenen, Alkinen und Carbenen, wobei jede Verbindungsklasse anhand ihrer Synthese, ihrer Reaktivität und ihres Koordinationstyps kurz vorgestellt wird. Des Weiteren werden besondere Elektronenkonfigurationen der Phosphorverbindungen behandelt, darunter P‐P‐Einelektronenbindungen, gespannte Bindungen und aromatische Systeme. Abschließend wird auf mögliche Anwendungen dieser Chemie zur Herstellung molekularer Materialien und in der homogenen Katalyse verwiesen.

show abstract

Section: Besondere Elektronenkonfigurationenunclassified

Phosphaorganische Chemie: Panorama und Perspektiven

Mathey

2003

Angewandte Chemie

198

View full text Add to dashboard Cite

show abstract

“…π-Complexes of unsaturated heterocycles exhibit frontier orbitals, which depend decisively on the heteroatom and the symmetry of the ring ligand, and these orbitals govern the reactivity of such complexes . We have utilized this effect for a significant variation of the properties of known catalysts with carbacyclic π ligands …”

Section: Introductionmentioning

confidence: 99%

1,2-Diphosphetene, 1,2-Diphosphete, and 1,3-Diphosphete Metal Complexes: Novel Access by Ring Contraction, Cyclodimerization, and Intramolecular Redox Reactions

et al. 1999

View full text Add to dashboard Cite

The reaction of [Cr(CO) 5 (THF)] and pentaphenyl-1,2,3-triphospholene affords a single stereoisomer of [(pentaphenyl-1,3-η-1,2,3-triphospholene)(Cr(CO) 5 ) 2 ] (6). Visible light photolysis of 6 causes a ring contraction and [(trans-tetraphenyl-1,2-η-1,2-diphosphetene)(Cr-(CO) 5 ) 2 ] (7a) is formed, whose stereochemistry was elucidated by X-ray crystallography. trans-1,2-Dichloro-3,4-di-tert-butyl-1,2-diphosphetene (2a) and [Fe 2 (CO) 9 ] form the σ complexes 8b), depending on the relative concentration of the starting materials. 8a has been proven to be an intermediate in the formation of 8b. Heating of neat 8b in a vacuum leads to the elimination of the chlorine substituents in an intramolecular redox reaction and [(3,4-di-tert-butyl-η 4 -1,2-diphosphete)-Fe(CO) 3 ] (9a) is formed. This is the first specific reaction, leading to a 1,2-diphosphete complex. 9a and its 1,3-isomer 10a react with [Cr(CO) 5 (THF)] to form the mono-and diaddition products [1-η-{(3,4-di-tert-butyl-η 4 -1,2-diphosphete)Fe(CO) 3 }Cr(CO) 5 ] (9b), [1,2-η-{(3,4-di-tert-butyl-η 4 -1,2-diphosphete)Fe(CO) 3 }(Cr(CO) 5 ) 2 ] (9c), [1-η-{(2,4-di-tert-butyl-η 4 -1,3-diphosphete)Fe(CO) 3 }Cr(CO) 5 ] (10b), and [1,3-η-{(2,4-di-tert-butyl-η 4 -1,3-diphosphete)-Fe(CO) 3 }(Cr(CO) 5 ) 2 ] (10c), respectively. X-ray crystallographic studies for 9c and 10c give some insight into the bonding situation of the compounds. σ-and π-complexing properties of the diphosphete ligands are almost independent of each other and significant back-bonding from the iron atom to the ligand π* orbitals occurs in both cases.

show abstract

“…Reactions with unsubstituted phosphinine and organoiron compounds have already been attempted, but only η 1 (σ)-complexation of the heterocycle was identified . The same is true for other transition metal complexes; only vanadium vapor and phosphinine directly yield (η 6 -phosphinine) 2 V …”

Section: Introductionmentioning

confidence: 99%

(η⁴-1,5-Cyclooctadiene)(η⁶-phosphinine)iron(0): Novel Room-Temperature Catalyst for Pyridine Formation^,¹

Knoch¹,

Kremer²,

Schmidt³

et al. 1996

Organometallics

106

View full text Add to dashboard Cite

Two routes are described for the synthesis of (η4-1,5-cyclooctadiene)(η6-phosphinine)iron(0) complexes. A three-component reaction of iron vapor with COD and 2-(trimethylsilyl)-4,5-dimethylphosphinine at low temperature yields 20% (COD)(2-(trimethylsilyl)-4,5-dimethylphosphinine)Fe(0) (3), whereas ligand exchange of one COD ligand of the in situ prepared metal vapor product (COD)2Fe by 2-(trimethylsilyl)-4,5-dimethylphosphinine or (η1-2-chloro-4,5-dimethylphosphinine)Cr(CO)5 gives corresponding (COD)(phosphinine)Fe(0) complexes in more than 80% isolated yield. As the phosphinine derivatives are prochiral, complexation leads to the racemate of two enantiomers. Both enantiomers are found in the unit cell of single crystalline 3 and are related by an inversion center. Complex 3 is a novel room-temperature catalyst for the [2 + 2 + 2] cyclic addition reaction of one molecule of butyronitrile with two molecules of methyl propargyl ether giving up to 160 mol of pyridine derivatives/mol 3. A chemically robust species, 3 is an air-stable crystalline material, but exposure to oxygen in solution causes slow decomposition.

show abstract

Bis(η⁶‐phosphabenzol)vanadium: Synthese, Redoxeigenschaften, Struktur und konformative Beweglichkeit

Cited by 24 publications

References 22 publications

Phosphaorganische Chemie: Panorama und Perspektiven

Phosphaorganische Chemie: Panorama und Perspektiven

1,2-Diphosphetene, 1,2-Diphosphete, and 1,3-Diphosphete Metal Complexes: Novel Access by Ring Contraction, Cyclodimerization, and Intramolecular Redox Reactions

(η⁴-1,5-Cyclooctadiene)(η⁶-phosphinine)iron(0): Novel Room-Temperature Catalyst for Pyridine Formation^,¹

Contact Info

Product

Resources

About

Bis(η6‐phosphabenzol)vanadium: Synthese, Redoxeigenschaften, Struktur und konformative Beweglichkeit

Cited by 24 publications

References 22 publications

Phosphaorganische Chemie: Panorama und Perspektiven

Phosphaorganische Chemie: Panorama und Perspektiven

1,2-Diphosphetene, 1,2-Diphosphete, and 1,3-Diphosphete Metal Complexes: Novel Access by Ring Contraction, Cyclodimerization, and Intramolecular Redox Reactions

(η4-1,5-Cyclooctadiene)(η6-phosphinine)iron(0): Novel Room-Temperature Catalyst for Pyridine Formation,1

Contact Info

Product

Resources

About

Bis(η⁶‐phosphabenzol)vanadium: Synthese, Redoxeigenschaften, Struktur und konformative Beweglichkeit

(η⁴-1,5-Cyclooctadiene)(η⁶-phosphinine)iron(0): Novel Room-Temperature Catalyst for Pyridine Formation^,¹