Fixierung von Luftstickstoff: Heterocyclensynthesen mit Luftstickstoff als Stickstoffquelle

Mori, Miwako; Hori, Katsutoshi; Akashi, Mitsuru; Hori, Masanori; Sato, Yoshiaki; Nishida, Motohiro

doi:10.1002/(sici)1521-3757(19980302)110:5<659::aid-ange659>3.3.co;2-k

Cited by 6 publications

(6 citation statements)

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“…The second strategy involves the search for high catalytic performance that revolves around the fine‐tuning of the ligand features capable of promoting subsequent transformations. A major recent advance in this direction is the catalytic formation of a remarkable variety of heterocyclic derivatives, as performed by in situ generated titanium‐based dinitrogen complexes 47. These remarkable transformations not only set the foundations for searching for other even more spectacular catalytic species, but also provide a greater stimulus towards understanding the unique chemical behavior of dinitrogen.…”

Section: Discussionmentioning

confidence: 99%

Multimetallic Cooperative Activation of N₂

2004

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The impressive number of breakthroughs reported in recent years in the field of dinitrogen activation reiterates the great interest that is still attracted by this molecule as a target for molecular activation studies. In spite of the fact that the discovery of dinitrogen fixation is rapidly approaching its 40th birthday, a thorough understanding of the factors that determine either fixation or activation is yet to be achieved. Nevertheless, substantial progress has recently been made. The aim of this article is to review some of the most recent literature and to assess the necessity of multimetallic attack to dinitrogen as a prerequisite towards further cleavage and functionalization.

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Section: Discussionmentioning

confidence: 99%

Multimetallic Cooperative Activation of N₂

2004

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“…In verschiedenen Reaktionen wird Li bereits zur Distickstoff‐Aktivierung eingesetzt. Beispielsweise wurde gefunden, dass sich mit einer Lösung von TiX 4 (X=Cl, O i Pr) in THF, die mit einem Überschuss an Me 3 SiCl und Li unter trockener Luft einen Tag gerührt und anschließend mit einer 10 %‐igen wässrigen HCl‐Lösung hydrolysiert und mit K 2 CO 3 ‐Lösung neutralisiert wurde, PhCOCl in hohen Ausbeuten zu PhCONH 2 umsetzen lässt 27. Die Autoren schlagen einen Komplex der Form [TiX m {N(SiMe 3 ) n } p ] als Zwischenstufe vor, die das Amid bindet, das sich nach Spaltung der N‐N‐Bindung durch das Li‐Metall zuvor gebildet hat.…”

Section: Valenzgesättigte Distickstoff‐komplexeunclassified

Intrinsische Stickstoff‐Aktivierung an “nackten” Metallatomen

Himmel

Reiher

2006

Angewandte Chemie

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Das Interesse an Metallkomplexen, die molekularen Stickstoff binden und seine Reduktion oder Oxidation unter milden Bedingungen bewirken, ist weiterhin ungebrochen. In der Natur katalysiert das Enzym Nitrogenase diesen Prozess. Unter milden Zellbedingungen findet die Distickstoff‐Fixierung an einem Metall‐Schwefel‐Cluster im Zentrum des MoFe‐Proteins statt. Details des Mechanismus sind jedoch weithin unbekannt, obwohl gerade in den letzten Jahren wichtige Entdeckungen in diesem Gebiet gemacht wurden. Im vorliegenden Aufsatz werden neueste Resultate über Wechselwirkungen von N2 mit Metallatomen und Metallatom‐Dimeren aller Gruppen des Periodensystems diskutiert, die vor allem in Gasphasen‐ und Matrixisolationsexperimenten gewonnen wurden. Die Relevanz dieser intrinsischen Distickstoff‐Aktivierung an ligandenfreien Metallatomen für die entsprechenden Reaktionen an Komplexen, Clustern und Oberflächen wird hervorgehoben.

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“…In addition to the metallocene‐based systems, Cp alternatives based on multidentate anionic ligands bearing N, O and P donor atoms were successfully used in order to obtain nitrogen complexes 17–25. It was also shown that the introduction of nitrogen into organic substrates becomes possible under reductive conditions 26–29…”

Section: Introductionmentioning

confidence: 99%

Low‐Valent Titanium–Pentafulvene Complexes — Formation of Dinuclear Titanium–Nitrogen Complexes

et al. 2005

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Sodium amalgam reduction of [(η5‐C5Me5)TiCl3] (1) in the presence of the pentafulvenes {C5H4=CR2, R: p‐tol (2), p‐FPh (3), CR2: adamantyl (4)} under nitrogen smoothly produces dark green or dark blue dinuclear low‐valent titanium complexes [{(η5‐C5Me5)Ti(η6‐C5H4=CR2)}2(μ2,η1,η1‐N2)] {R: p‐tol (6), p‐FPh (7), CR2: adamantyl (8)}, characterized by a bridging end‐on coordinated dinitrogen ligand, in high yield. In the same way, the nitrogen‐free, low‐coordinated complex [(η5‐C5Me5)Ti(η6‐C9H6=C(p‐tol)2)] (10) is obtained by using the more sterically demanding benzofulvene C9H6=C(p‐tol)2 (5) instead of 2–4. The solid‐state structures of the dinitrogen compounds reveal weakly activated end‐on bound N2 ligands with identical N–N distances of 1.160(3) Å (6) and 1.160(5) Å (8). The dinitrogen complexes 6, 7 and 8 show diamagnetic behaviour, which allowed a complete NMR spectroscopic characterization. So a correlation between the situation in solution, measured by NMR, and in the solid state (X‐ray diffraction) becomes possible and shows a congruent picture. A broad range of reactions can be imagined concerning the easily replaceable dinitrogen ligand as well as the known reactivity of fulvene ligands in complexes of early transition metals. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Fixierung von Luftstickstoff: Heterocyclensynthesen mit Luftstickstoff als Stickstoffquelle

Cited by 6 publications

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Multimetallic Cooperative Activation of N₂

Multimetallic Cooperative Activation of N₂

Intrinsische Stickstoff‐Aktivierung an “nackten” Metallatomen

Low‐Valent Titanium–Pentafulvene Complexes — Formation of Dinuclear Titanium–Nitrogen Complexes

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Fixierung von Luftstickstoff: Heterocyclensynthesen mit Luftstickstoff als Stickstoffquelle

Cited by 6 publications

References 0 publications

Multimetallic Cooperative Activation of N2

Multimetallic Cooperative Activation of N2

Intrinsische Stickstoff‐Aktivierung an “nackten” Metallatomen

Low‐Valent Titanium–Pentafulvene Complexes — Formation of Dinuclear Titanium–Nitrogen Complexes

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Multimetallic Cooperative Activation of N₂

Multimetallic Cooperative Activation of N₂