1,2,4-Triazole-3,5-diylidene:  A Building Block for Organometallic Polymer Synthesis

Guerret, Olivier; Solé, Stéphane; Gornitzka, Heinz; Teichert, Markus; Trinquier, Georges; Bertrand, Guy

doi:10.1021/ja964191a

Cited by 211 publications

(134 citation statements)

References 28 publications

Supporting

Mentioning

122

Contrasting

Unclassified

Order By: Relevance

“…The shortest interconnection of metal centers by a ditopic NHC ligand has been realized by Bertrand and 420 coworkers upon metalation of the triazol-diylidene precursor 38, affording the linear silver carbene polymer 39 (Scheme 5). 43 The carbene linker has been expanded by Bielawski (Fig. 11) which provided evidence for non-negligible π contribution to the M-C NHC bond, and for the tunability of these π interactions.…”

Section: Organometallic Polymers Comprising Nheterocyclic Carbene Commentioning

confidence: 99%

Beyond catalysis: N-heterocyclic carbene complexes as components for medicinal, luminescent, and functional materials applications

2010

View full text Add to dashboard Cite

Section: Organometallic Polymers Comprising Nheterocyclic Carbene Commentioning

confidence: 99%

Beyond catalysis: N-heterocyclic carbene complexes as components for medicinal, luminescent, and functional materials applications

2010

View full text Add to dashboard Cite

“…A-C, Figure 1). [15] However, even in complexes containing Abstract: A ditopic benzobisA C H T U N G T R E N N U N G (carbene) ligand precursor was prepared that contained a chelating pyridyl moiety to ensure co-planarity of the carbene ligand and the coordination plane of a bound octahedral metal center. Bimetallic ruthenium complexes comprising this ditopic ligand [L 4 Ru-C,N-bbi-C,N-RuL 4 ] were obtained by a transmetalation methodology (C,N-bbi-C,N = benzobis(N-pyridyl-N'-methyl-imidazolylidene).…”

Section: Introductionmentioning

confidence: 99%

“…While HPLC-MS analysis suggests a pure compound, NMR spectroscopic analysis shows two distinct sets of signals that were attributed to the rac and meso diastereoisomers of 5 as a consequence of the chirality of the complex at each ruthenium center. [15,24] Solubility tests revealed that one of the two isomers is less soluble in MeCN and was thus successfully separated by repetitive precipitation and filtration. This isomer is stable in solution over several days, which demonstrates that racemization at ruthenium is very slow.…”

mentioning

confidence: 99%

Efficient Electronic Communication of Two Ruthenium Centers through a Rigid Ditopic N‐Heterocyclic Carbene Linker

Nussbaum

Schuster

Albrecht

2013

Chemistry A European J

View full text Add to dashboard Cite

A ditopic benzobis(carbene) ligand precursor was prepared that contained a chelating pyridyl moiety to ensure co‐planarity of the carbene ligand and the coordination plane of a bound octahedral metal center. Bimetallic ruthenium complexes comprising this ditopic ligand [L4Ru‐C,N‐bbi‐C,N‐RuL4] were obtained by a transmetalation methodology (C,N‐bbi‐C,N=benzobis(N‐pyridyl‐N′‐methyl‐imidazolylidene). The two metal centers are electronically decoupled when the ruthenium is in a pseudotetrahedral geometry imparted by a cymene spectator ligand (L4=[(cym)Cl]). Ligand exchange of the Cl−/cymene ligands for two bipyridine or four MeCN ligands induced a change of the coordination geometry to octahedral. As a consequence, the ruthenium centers, separated through space by more than 10 Å, become electronically coupled, which is evidenced by two distinctly different metal‐centered oxidation processes that are separated by 134 mV (L4=[(bpy)2]; bpy=2,2′‐bipyridine) and 244 mV (L4=[(MeCN)4]), respectively. Hush analysis of the intervalence charge‐transfer bands in the mixed‐valent species indicates substantial valence delocalization in both complexes (delocalization parameter Γ=0.41 and 0.37 in the bpy and MeCN complexes, respectively). Spectroelectrochemical measurements further indicated that the mixed‐valent RuII/RuIII species and the fully oxidized RuIII/RuIII complexes gradually decompose when bound to MeCN ligands, whereas the bpy spectators significantly enhance the stability. These results demonstrate the efficiency of carbenes and, in particular, of the bbi ligand scaffold for mediating electron transfer and for the fabrication of molecular redox switches. Moreover, the relevance of spectator ligands is emphasized for tailoring the degree of electronic communication through the benzobis(carbene) linker.

show abstract

“…The first attempt to obtain such complexes was carried out by Bertrand and co-authors 43 by treatment of 1,2,4-trimethyl-1,2,4-triazolium biscation bistriflate with silver acetate.…”

Section: Heteroaromatic Biscarbenes Of the 124-triazole Seriesmentioning

confidence: 99%

Stable heteroaromatic carbenes of the benzimidazole and 1,2,4-triazole series

Коротких¹,

Shvaika²,

Rayenko³

et al. 2005

Arkivoc

View full text Add to dashboard Cite

The review is focused on new data concerning the syntheses and selected properties of stable heteroaromatic monocarbenes of the benzimidazole and 1,2,4-triazole series, biscarbenes, anionocarbenes of the 1,2,4-triazole series, and cryptocarbenes. The syntheses of the precursors to these compounds are also described. Special attention is paid to C-H insertion reactions, X-ray structural data and spectral characteristics of the carbenes and their analogues.

show abstract

1,2,4-Triazole-3,5-diylidene: A Building Block for Organometallic Polymer Synthesis

Cited by 211 publications

References 28 publications

Beyond catalysis: N-heterocyclic carbene complexes as components for medicinal, luminescent, and functional materials applications

Beyond catalysis: N-heterocyclic carbene complexes as components for medicinal, luminescent, and functional materials applications

Efficient Electronic Communication of Two Ruthenium Centers through a Rigid Ditopic N‐Heterocyclic Carbene Linker

Stable heteroaromatic carbenes of the benzimidazole and 1,2,4-triazole series

Contact Info

Product

Resources

About