Calcium-mediated fulvene couplings. 3. Reductive coupling of guaiazulene with activated calcium to give a mixture of 8,6′ and 8,8′ (diguaiazulenide)calcium isomers. Thermal rearrangement of the 8,6′ isomer to the 8,8′ isomer and X-ray crystal structure of the 8,8′ isomer

Sinnema, Piet-Jan; Shapiro, Pamela J.; Höhn, Britta; Twamley, Brendan

doi:10.1016/s0022-328x(03)00310-3

Cited by 13 publications

(1 citation statement)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…296.9 [d] ;2 97.9 [d] 297.1 [d] ;3 08.1 In addition to metallocenophanes of magnesium, there are severale xamples of metallocenophanes of the heaviera lkaline earth metals calcium, strontium and barium, witht he majority being calcocenophanes, 2 (Figure 4). [36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53] In contrast to magnesocenophanes, 1,w here the synthesis commonly involves metalation of an ansa-ligand system by deprotonation with dibutyl magnesium( Scheme1), calcocenophanes, 2,a nd strontiocenophane, 3,a re often prepared by oxidative coupling startingf rom the corresponding alkaline earth metal and a suitablef ulvene (Scheme5). [38][39][40][41][42][43][44][45][46][47][48][49][50][51][52] Activated calcium or strontium metal reacts with as uitable fulvene in ad onor solvent, such as thf, and gives the corre-spondingC [2]metallocenophane, as first demonstrated by Edelmann et al in 1993.…”

Section: Compoundmentioning

confidence: 99%

Main‐Group Metallocenophanes

Wirtz

Schäfer

2020

Chemistry A European J

View full text Add to dashboard Cite

Metallocenes with interlinked cyclopentadienidel igands are commonly referred to as ansa-metallocenes or metallocenophanes.T hese can have drastically different properties than their unbridged parentc ompounds. While this concept is best known for transition metalss uch as iron, it can also be adopted form any main-group elements. This review aims to summarize recent advances in the field of metallocenophanes based on main-group elements of group 2, group 13, group 14 and group 15, focusingo ns ynthesis, structure and properties of these compounds.

show abstract

Section: Compoundmentioning

confidence: 99%

Main‐Group Metallocenophanes

Wirtz

Schäfer

2020

Chemistry A European J

View full text Add to dashboard Cite

show abstract

Cyclopentadienyl Complexes of the Alkaline Earths in Light of the Periodic Trends

Baguli

Mondal

Mandal

et al. 2021

Chemistry An Asian Journal

View full text Add to dashboard Cite

The electron‐rich cyclopentadienyl and the analogous indenyl and fluorenyl ligands (collectively denoted here as Cp’) have been impactful in stabilizing electron‐deficient metal centers including the highly electropositive alkaline earths. Being in the s‐block, the group 2 metals follow a major periodic variation in their atomic and ionic properties which is reflected in those Cp’ compounds. This article presents an overview of this class of compounds for all the five metals from beryllium to barium (radium is excluded for its radioactivity), highlighting their systematic variation.

show abstract

Alkali‐Metal Aminotroponiminates: Selectivities and Equilibria in Reversible Radical Coupling of Delocalized π‐Electron Systems

Hanft

Krummenacher

Lichtenberg

2019

Chemistry A European J

View full text Add to dashboard Cite

Aminotroponiminates (ATIs) have recently been shown to belong to the growing class of redox‐active ligands. The choice of the metal center allowed to switch between reversible electron transfer (M=Rh) and reductively induced dimerization (M=Na). Here, we investigate if the reductively induced dimerization of ATIs is a more general phenomenon for their alkali‐metal complexes. Lithium ATI complexes are shown to undergo reductively induced dimerizations, which are equilibrium reactions and chemically reversible. The choice of the metal center (Li vs. Na), the substitution pattern at the nitrogen atoms of the ATI ligands, and the solvent critically influence the regioselectivity and diastereoselectivity of the radical‐dimerization reactions. Potassium ATIs are shown to be susceptible to side reactions, more specifically a reduction accompanied by hydrogen‐atom transfer. Products and intermediates of the reductively induced dimerizations were characterized by techniques including NMR and EPR spectroscopy, cyclic voltammetry, DFT calculations, single‐crystal X‐ray diffraction, and mass spectrometry.

show abstract

Calcium-mediated fulvene couplings. 3. Reductive coupling of guaiazulene with activated calcium to give a mixture of 8,6′ and 8,8′ (diguaiazulenide)calcium isomers. Thermal rearrangement of the 8,6′ isomer to the 8,8′ isomer and X-ray crystal structure of the 8,8′ isomer

Cited by 13 publications

References 18 publications

Main‐Group Metallocenophanes

Main‐Group Metallocenophanes

Cyclopentadienyl Complexes of the Alkaline Earths in Light of the Periodic Trends

Alkali‐Metal Aminotroponiminates: Selectivities and Equilibria in Reversible Radical Coupling of Delocalized π‐Electron Systems

Contact Info

Product

Resources

About