[Cp*Fe(η5‐P5)], ein Sandwichkomplex mit vielfältigen Ligandeneigenschaften

Detzel, Michaela; Mohr, Thomas; Scherer, Otto J.; Wolmershäuser, Gotthelf

doi:10.1002/ange.19941061011

Cited by 37 publications

(7 citation statements)

References 13 publications

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“…As a result of the twofold reduction, the cyclo-P 5 unit adopts an envelope conformation. [27] In the thus-obtained {Cp*FeP 5 } 2À anion, the phosphorus ligand may be considered as a formally cyclo-P 5 3À polyphosphide anion, which can be understood in the following way: One negative charge is localized on the phosphorus atom, which is bent out of plane, whereas the remaining negative charges are delocalized over the other four phosphorus atoms and the {Cp*Fe} fragment. Formally, the cyclo-P 5 unit binds in a h 4 -coordination mode to the iron atom.…”

Section: àmentioning

confidence: 99%

Mixed‐Metal Lanthanide–Iron Triple‐Decker Complexes with a cyclo‐P₅ Building Block

Wiecko

Pushkarevsky

et al. 2011

Angew Chem Int Ed

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Triple-and multidecker sandwich complexes have been discussed in the last decades for their unique electrical and magnetic properties. The organic spacer between the metals may facilitate intermetallic electronic communication, which has a high potential for molecular electronics.[1] A number of one-dimensional organometallic sandwich molecular wires (SMWs) have been extensively studied. Thus, the multilayer vanadium-arene (Ar) organometallic complexes [V n (Ar) m ], which can be produced in a molecular beam by laser vaporization, are a class of one-dimensional molecular magnets.[2] Ferrocene-based molecular wires have been synthesized in the gas phase and characterized by mass spectroscopy.[3] It was calculated that these compounds have half-metallic properties with 100 % negative spin polarization near the Fermi level in the ground state.[4] In contrast to this investigation in the gas phase, studies on related organometallic triple-and multidecker sandwich complexes containing f-block elements (lanthanides or actinides) in condensed phase remain rare;[5] studies were mostly on the cyclooctatetraene ligand and its derivatives. The only rare-earth-element triple-decker complex with heterocycles is the low-valent scandium 1,3,5-triphosphabenzene complex [{(h 5 -P 3 C 2 tBu 2 )Sc} 2 (m-h 6 :h 6 -P 3 C 3 tBu 3 )], which was obtained by cocondensation of scandium vaporized in an electron beam with an excess of the phosphaalkyne tBuCP.[6] Apart from organometallic compounds, triple-and multidecker sandwich complexes of the 4f elements consisting of "salen" type Schiff base ligands, [7] phthalocyanines, and porphyrins have been extensively studied because these compounds exhibit tunable spectroscopic, electronic, and redox properties, and different extents of intramolecular p-p interactions.[8] Despite these promising physical properties further investigations on 4f elements based triple-and multidecker sandwich complexes are obviously hampered by the limited variety of ligands that have been attached to the metal centers to date. Based on these considerations, we present herein mixed d/f-block-metal triple-decker complexes with a purely inorganic all-phosphorus middle deck.In contrast to d-block chemistry, where purely inorganic ring systems of Group 15 elements such as P 5 and P 6 , [9] As 5 , [9c] and Sb 5 [10] are well-established, there is no analogy with the fblock elements to date. On the other hand, it was shown only recently that rare-earth elements can stabilize highly reactive main-group species such as N 2 3À .[11] Although some heavier Group 15-lanthanide compounds, such as phosphides (Ln À PR 2 ), [12] arsenides (Ln À AsR 2 ), [12d, 13] stibides (Ln À Sb 3 ), [14] and bismutides (LnÀBiÀBiÀLn) [15] are known, the first molecular polyphosphide of the rare-earth elements, [(Cp* 2 Sm) 4 P 8 ] (Cp* = h 5 -C 5 Me 5 ), was recently synthesized. [16] The structure of the complex is very rare and can be described as a realgartype P 8 4À ligand trapped in a cage of four samarocenes. As no triple-decker sandw...

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Section: àmentioning

confidence: 99%

Mixed‐Metal Lanthanide–Iron Triple‐Decker Complexes with a cyclo‐P₅ Building Block

Wiecko

Pushkarevsky

et al. 2011

Angew Chem Int Ed

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“…Pentaphosphaferrocenes (5) are readily available in a single step starting from P 4 and the dicarbonyl(pentamethylcyclopentadienyl)iron dimer [{(C 5 Me 5 )Fe(CO) 2 } 2 ] (or similar derivatives with different Cp substituent pattern) [22] and have been shown to be versatile starting compounds for a variety of oligonuclear P n complexes [23]. The reaction of [(C 5 H 2 t Bu 3 -1,2,4)Mo(CO) 3 CH 3 ] (6) with [(C 5 Me 5 )Fe(g 5 -P 5 )] (5a) produced a complicated mixture of complexes including the 1:2 product [(C 5 Me 5 )-Fe(l 3 ,g 4 :g 1 :g 1 -P 7 CH 3 ){Fe(CO)(C 5 Me 5 )}(l,g 3 :g 1 -P 3 ){Mo (CO)(C 5 H 2 t Bu 3 -1,2,4)}] (7) with a norbornadiene-like P 7 cage containing a methyl group on the bridging P atom (Fig.…”

Section: Metal-mediated Transfer Of Alkyl Groups To Naked Phosphorus mentioning

confidence: 99%

Functionalization of white phosphorus in the coordination sphere of transition metal complexes

Peruzzini

Abdreimova²,

Budnikova

et al. 2004

Journal of Organometallic Chemistry

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“…Als Folge der zweifachen Reduktion nimmt die cyclo-P 5 -Einheit eine Briefumschlagkonformation ein. [27] Im so erhaltenen {Cp*FeP 5 } 2À -Anion kann der Phosphorligand formal als cyclo-P 5…”

Section: Nahinfrarot(nir-)spektroskopie Bestimmt Die Geringe Paramagunclassified

Gemischte Lanthanoid‐Eisen‐Tripeldeckerkomplexe mit einem cyclo‐P₅‐Baustein

Wiecko

Pushkarevsky

et al. 2011

Angewandte Chemie

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P‐Ring mittendrin: Gemischte d/f‐Metall‐Tripeldeckerkomplexe mit rein anorganischem Mitteldeck waren bislang unbekannt. Hier wird ein gemischter Eisen‐Samarium‐Komplexe mit einem cyclo‐P5‐Polyphosphid zwischen den Metallzentren vorgestellt [siehe Struktur; klein schwarz C, blau Fe, grün N, rot O, pink P, groß schwarz Sm]. Je nach Reaktionsbedingungen wird diese Verbindung als Monomer oder Dimer erhalten.

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[Cp^*Fe(η⁵‐P₅)], ein Sandwichkomplex mit vielfältigen Ligandeneigenschaften

Abstract: lo] Alle Berechnungen wurden rnit dem Progammpaket VAMP 4.5 [I I] ohne Symrnetrierestriktionen auf Restricted-Hartree-Fock (RHF)-Niveau durchgefuhrt. Die berechneten Geometrien wurden durch Schwingungsanalysen als Minima auf der Energiehyperflache charakterisiert.

Cited by 37 publications

References 13 publications

Mixed‐Metal Lanthanide–Iron Triple‐Decker Complexes with a cyclo‐P₅ Building Block

Mixed‐Metal Lanthanide–Iron Triple‐Decker Complexes with a cyclo‐P₅ Building Block

Functionalization of white phosphorus in the coordination sphere of transition metal complexes

Gemischte Lanthanoid‐Eisen‐Tripeldeckerkomplexe mit einem cyclo‐P₅‐Baustein

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[Cp*Fe(η5‐P5)], ein Sandwichkomplex mit vielfältigen Ligandeneigenschaften

Abstract: lo] Alle Berechnungen wurden rnit dem Progammpaket VAMP 4.5 [I I] ohne Symrnetrierestriktionen auf Restricted-Hartree-Fock (RHF)-Niveau durchgefuhrt. Die berechneten Geometrien wurden durch Schwingungsanalysen als Minima auf der Energiehyperflache charakterisiert.

Cited by 37 publications

References 13 publications

Mixed‐Metal Lanthanide–Iron Triple‐Decker Complexes with a cyclo‐P5 Building Block

Mixed‐Metal Lanthanide–Iron Triple‐Decker Complexes with a cyclo‐P5 Building Block

Functionalization of white phosphorus in the coordination sphere of transition metal complexes

Gemischte Lanthanoid‐Eisen‐Tripeldeckerkomplexe mit einem cyclo‐P5‐Baustein

Contact Info

Product

Resources

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[Cp^*Fe(η⁵‐P₅)], ein Sandwichkomplex mit vielfältigen Ligandeneigenschaften

Mixed‐Metal Lanthanide–Iron Triple‐Decker Complexes with a cyclo‐P₅ Building Block

Mixed‐Metal Lanthanide–Iron Triple‐Decker Complexes with a cyclo‐P₅ Building Block

Gemischte Lanthanoid‐Eisen‐Tripeldeckerkomplexe mit einem cyclo‐P₅‐Baustein