Reduktion eines 1‐Aza‐1,3‐diens zum 1‐Azabut‐2‐en‐1,4‐diyl‐Dianion: ein ungewöhnlicher Reaktionsverlauf

Lorenz, Volker; Görls, Helmar; Scholz, Joachim

doi:10.1002/ange.200250116

Cited by 5 publications

(1 citation statement)

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“…Dilithium but-2-ene-1,4-diyl derivatives such as [{C 4 H 4 (SiMe 3 ) 2 }{Li(THF) 2 } 2 ] can also be used for transferring dianionic diene ligands to transition metals. However, to our knowledge no efforts have been made so far to explore the preparation of magnesium 1-aza-1,3-diene compounds, and only recently we reported for the first time the reaction of the 1-aza-1,3-diene ( i Pr)NCHC(Me)CH(Ph) with lithium. , Thus, most of the 1-aza-1,3-diene complexes of early transition metals known up to now have been prepared by simple reduction of transition-metal halides by magnesium or lithium in the presence of 1-aza-1,3-dienes …”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structure of the First Homoleptic 1-Aza-1,3-diene Titanium Complex: A Tightrope Walk between Ligand Coordination and Ligand Coupling

2004

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The reaction of TiCl 4 (THF) 2 or ZrCl 4 (THF) 2 with Mg in the presence of 1-aza-1,3-dienes (1) has been investigated. Reduction of TiCl 4 (THF) 2 with 2 equiv of Mg in the presence of 2 equiv of (R 1 )NdCHC(R 2 )dCH(Ph) yields the first homoleptic 1-aza-1,3-diene complex, [Ti-{N(R 1 )CHdC(R 2 )CH(Ph)} 2 ] (7), but only if the 1-aza-1,3-diene is substituted by a sterically demanding group at the nitrogen atom (1b: R 1 ) C 6 H 3 -2,6-iPr 2 , R 2 ) H). X-ray crystallography indicates a σ 2 ,π coordination of the heterodienes, which are reduced to 1-azabut-2-ene-1,4-diyl dianions to form folded 1-aza-2-titanacyclopent-4-ene rings. As a byproduct, the bicyclic complex [{N(R 1 )CHdC(R 2 )CH(Ph)}Ti{N(R 1 )CHdC(R 2 )CH(Ph)CH{C(R 2 )dCH-(Ph)}N(R 1 )] (8) was isolated, which is believed to arise from CdN insertion of 1b into the Ti-C bond of the intermediate [{N(R 1 )CHdC(R 2 )CH(Ph)}TiCl 2 ], followed by the coordination of a further 1-aza-1,3-diene ligand. The analogous bicyclic zirconium complex [{N(R 1 )CHd C(R 2 )CH(Ph)}Zr{N(R 1 )CHdC(R 2 )CH(Ph)CH{C(R 2 )dCH(Ph)}N(R 1 )] (6: R 1 ) cyclo-C 6 H 11 , R 2 ) Me) is the only available product when the reduction of ZrCl 4 (THF) 2 is performed in the presence of the 1-aza-1,3-diene (cyclo-C 6 H 11 )NdCHC(Me)dCHPh (1a), which is substituted by a sterically less demanding group at the terminal nitrogen atom. Addition of 2 equiv of benzophenone to 7 affords the titanium complex [Ti{OCPh 2 CH(Ph)C(R 2 )dCHN(R 1 )} 2 ] (9). The solid-state structure of 9 shows the titanium in a distorted-tetrahedral environment, being the center of two folded oxazatitanacycloheptene rings.

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Section: Introductionmentioning

confidence: 99%

Synthesis and Structure of the First Homoleptic 1-Aza-1,3-diene Titanium Complex: A Tightrope Walk between Ligand Coordination and Ligand Coupling

2004

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Expandierte Porphyrine: überraschende Strukturen, elektronische Eigenschaften und Reaktivitäten

2011

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Die Chemie von expandierten Porphyrinen, den höheren Homologen der Porphyrine, wurde im Laufe der letzten drei Jahrzehnte ausgiebig untersucht. Expandierte Porphyrine weisen Strukturen, elektronische Eigenschaften, Reaktivitäten und ein Koordinationsverhalten auf, die sich gänzlich von denen der Porphyrine unterscheiden. Im Laufe dieser Untersuchungen wurde immer deutlicher, dass expandierte Porphyrine im Hinblick auf ihre Aromatizität und die Koordination an mehrere Metallionen oder als funktionelle Farbstoffe, nichtlinear‐optische Materialien, Ionenrezeptoren, stabile organische Radikale und vieles mehr äußerst attraktiv sind. Kontinuierlich tauchen expandierte Porphyrine mit überraschenden neuen Strukturen und Eigenschaften auf. Letzteres wird durch die einfache Synthese Möbius‐aromatischer und sogar antiaromatischer Systeme mit verdrillten Molekülstrukturen besonders deutlich. Hier werden Fortschritte auf dem Gebiet der expandierten Porphyrine seit dem Erscheinen des Aufsatzes von Sessler und Seidel im Jahr 2003 dargelegt.

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Expanded Porphyrins: Intriguing Structures, Electronic Properties, and Reactivities

2011

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The chemistry of expanded porphyrins, which are higher homologues of porphyrins, has been intensively explored for the last three decades. Expanded porphyrins exhibit structures, electronic properties, coordination chemistry, and reactivities that are entirely different from those of porphyrins. Through these studies, it has become increasingly apparent that expanded porphyrins are attractive in views of aromaticity and multimetal coordination, or as functional dyes, nonlinear optical materials, ion receptors, or stable organic radicals. As such, we have continuously witnessed the emergence of expanded porphyrins that exhibit unprecedented structures and properties, as is highlighted by the facile realization of Möbius aromatic and even antiaromatic systems with twisted molecular structures. In this Review, the recent progress of the chemistry of expanded porphyrins after the seminal Review by Sessler and Seidel in 2003 is presented.

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Reduktion eines 1‐Aza‐1,3‐diens zum 1‐Azabut‐2‐en‐1,4‐diyl‐Dianion: ein ungewöhnlicher Reaktionsverlauf

Cited by 5 publications

References 26 publications

Synthesis and Structure of the First Homoleptic 1-Aza-1,3-diene Titanium Complex: A Tightrope Walk between Ligand Coordination and Ligand Coupling

Synthesis and Structure of the First Homoleptic 1-Aza-1,3-diene Titanium Complex: A Tightrope Walk between Ligand Coordination and Ligand Coupling

Expandierte Porphyrine: überraschende Strukturen, elektronische Eigenschaften und Reaktivitäten

Expanded Porphyrins: Intriguing Structures, Electronic Properties, and Reactivities

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