C<sub>4</sub> Cumulene and the Corresponding Air‐Stable Radical Cation and Dication

Li, Yan; Mondal, Kartik Chandra; Samuel, Prinson P.; Zhu, Hongping; Orben, Claudia M.; Panneerselvam, S.; Dittrich, Birger; Schwederski, Brigitte; Kaim, Wolfgang; Mondal, Totan; Koley, Debasis; Roesky, Herbert W.

doi:10.1002/anie.201310975

Cited by 119 publications

(92 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Even more recently, the C 2 unit has been interpreted as a -acceptor and -donor Lewis acid with respect to CAACs [107,108] or pyridylidenes [109] in the stable butatriene derivatives 1 and 2, respectively (Fig. 4).…”

Section:  1 -Alkynyl -Complexesmentioning

confidence: 99%

See 1 more Smart Citation

On the nature of the dative bond: Coordination to metals and beyond. The carbon case

Lepetit

Maraval

Canac

et al. 2016

Coordination Chemistry Reviews

View full text Add to dashboard Cite

Section:  1 -Alkynyl -Complexesmentioning

confidence: 99%

“…Butatrienes derivatives where CAACs are regarded as stabilizators of the « bare » C 2 unit[107][108][109].…”

mentioning

confidence: 99%

On the nature of the dative bond: Coordination to metals and beyond. The carbon case

Lepetit

Maraval

Canac

et al. 2016

Coordination Chemistry Reviews

View full text Add to dashboard Cite

“…For example, they can be used as molecular wires [31][32][33][34] as their conductivity is significantly better than the other possible form of linear carbon chains,p olyynes. [32,35,36] Strong s donors as end-capping groups of the cumulene chain give their radical speciesaremarkable stability, [26,32,[37][38][39][40] with someo ft hese radicals stable even to air. [39,40] Cumulenes have been known for around100 years, [41] however, [3]cumulenes that have strong s donors as terminal groups, such as N-heterocyclic or cyclic (alkyl)(amino) carbenes (NHCs or CAACs, respectively), have only recently been studied.…”

Section: Introductionmentioning

confidence: 99%

How to Bend a Cumulene

Barquera‐Lozada

2020

Chemistry A European J

View full text Add to dashboard Cite

Allenes (carbodicarbenes) and [3]cumulenes are linear carbon chains that can be bent when the terminal group has a strong carbene nature. This bending can be quite pronounced in allenes but not in [3]cumulenes. In this study, how N‐heterocyclic or cyclic (alkyl)(amino) carbene (NHC and CAAC, respectively) terminal groups can modify the linear structure of [n]cumulenes has been analyzed. A low π acidity of the terminal carbene affects the linearity of [2n]cumulenes. Indeed, it has been found that the NHC [4]cumulene is extremely bent, contrary to classical [4]cumulenes. The predicted NHC [4]cumulene or tricarbodicarbene has two lone pairs and the π electrons are delocalized over the whole molecule. More significantly, DFT calculations have shown that this bent [4]cumulene is very stable, considerably more so than the corresponding [3]cumulene, which has been elusive to synthesize. Remarkably, calculations have shown that all the NHC [2n]cumulenes are more than 25 kcal mol−1 more stable than the [2n−1]cumulenes.

show abstract

“…Among them are electronic (UV/Vis), vibrational (infrared and Raman), nuclear magnetic resonance (NMR), and electron paramagnetic resonance (EPR) spectroscopy. The latter—also called electron spin resonance (ESR) spectroscopy—has proved to be indispensable in studies of radical species, which attract the attention of researchers due to their important roles in physics, chemistry, biochemistry, environmental, and material science …”

Section: Introductionmentioning

confidence: 99%

Density functional theory and ab initio studies on hyperfine coupling constants of phosphinyl radicals

Witwicki

2018

Int J of Quantum Chemistry

View full text Add to dashboard Cite

The 31P hyperfine coupling constants for various phosphinyl radicals were calculated using density functional theory (DFT) as well as the ab initio orbital‐optimized spin‐component‐scaled MP2 (OO‐SCS‐MP2) and coupled cluster methods (with relaxed and unrelaxed density). However before that, electron correlation in phosphinyl radicals was investigated by means of the fractional occupation number weighted electron density (FOD). The isotropic hyperfine coupling constants for phosphinyl radicals posed a considerable challenge to DFT; among other issues, the well‐known functional B3LYP substantially underperformed, but TPSS0 provided highly accurate results. Two tested double hybrid functionals, namely B2PLYP and mPW2PLYP, and OO‐SCS‐MP2 were found to be reasonably accurate. The unbalanced description of spin polarization in the valance region was identified as the root of the problems of DFT methods with correct prediction of the isotropic hyperfine coupling constants. In calculations at the coupled cluster level, relaxed and unrelaxed density matrices were tested and both were proved to provide highly satisfactory results for phosphinyl radicals. This was confirmed for a set of small paramagnetic species.

show abstract

C₄ Cumulene and the Corresponding Air‐Stable Radical Cation and Dication

Cited by 119 publications

References 45 publications

On the nature of the dative bond: Coordination to metals and beyond. The carbon case

On the nature of the dative bond: Coordination to metals and beyond. The carbon case

How to Bend a Cumulene

Density functional theory and ab initio studies on hyperfine coupling constants of phosphinyl radicals

Contact Info

Product

Resources

About

C4 Cumulene and the Corresponding Air‐Stable Radical Cation and Dication

Cited by 119 publications

References 45 publications

On the nature of the dative bond: Coordination to metals and beyond. The carbon case

On the nature of the dative bond: Coordination to metals and beyond. The carbon case

How to Bend a Cumulene

Density functional theory and ab initio studies on hyperfine coupling constants of phosphinyl radicals

Contact Info

Product

Resources

About

C₄ Cumulene and the Corresponding Air‐Stable Radical Cation and Dication