2010
DOI: 10.1002/chem.201000396
|View full text |Cite
|
Sign up to set email alerts
|

Demonstration of “Möbius” Aromaticity in Planar Metallacycles

Abstract: Möbius aromaticity, predicted by Edgar Heilbronner in 1964, is a stabilizing effect exhibited by 4n electron fully conjugated cyclic molecules (or transition states) with an odd number of orbital phase inversions. Although it has previously been suggested that this effect might also apply to planar metallacycles in which a transition metal employs a d orbital in delta-type binding mode, only very few examples of stable twisted molecules composed of main group elements are known. We report herein, the first com… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
2
1

Citation Types

5
108
0

Year Published

2010
2010
2022
2022

Publication Types

Select...
5
3

Relationship

0
8

Authors

Journals

citations
Cited by 102 publications
(113 citation statements)
references
References 102 publications
5
108
0
Order By: Relevance
“…Our achievement reveals that the Möbius aromaticity in osmapentalynes is rooted in osmapentalenes. As Craig-Möbius aromaticity 26,27 was first proposed in 1958, authentic examples of planar Möbius aromaticity are very rare. The realization of osmapentalynes 19 and osmapentalenes has widened the scope of Möbius aromaticity significantly and opens a new avenue for the construction of other planar Möbius aromatic complexes.…”
Section: Discussionmentioning
confidence: 99%
See 1 more Smart Citation
“…Our achievement reveals that the Möbius aromaticity in osmapentalynes is rooted in osmapentalenes. As Craig-Möbius aromaticity 26,27 was first proposed in 1958, authentic examples of planar Möbius aromaticity are very rare. The realization of osmapentalynes 19 and osmapentalenes has widened the scope of Möbius aromaticity significantly and opens a new avenue for the construction of other planar Möbius aromatic complexes.…”
Section: Discussionmentioning
confidence: 99%
“…This metal fragment not only relieves considerable ring strain in pentalyne, but also results in Möbius aromatic stabilization of the rarely realized planar Craig type, which was first proposed by Craig by analysing the interactions of d-atomic orbitals (AOs) present in an alternating cyclic array of main group pp-dp AOs by reference to trimeric and tetrameric phosphonitric chlorides 26 and was later extended to transition metal-containing 4n p metallacycles by Mauksch and Tsogoeva computationally 27 . Interestingly, the metal-carbon triple bond in osmapentalynes can shift from one five-membered ring to another 19 .…”
mentioning
confidence: 99%
“…Through density functional theory (DFT) calculations, we revealed that these organometallics exhibit Craig-type Möbius aromaticity resulting from eight-center eight-electron (8c-8e) d π -p π conjugation. Note that such Craig-type Möbius aromaticity was computationally demonstrated in 4nπ planar metallacycles early in 2010 by Mauksch and Tsogoeva 33 and in osmasilapentalyne 34 and dimetalla 10 annulenes by us 35 . However, the aromaticity of these novel organometallics in the excited-state has not been reported so far.…”
mentioning
confidence: 90%
“…In fact, the two p-conjugation topologies can even coexist, as was suggested in earlier work on aromaticity of planar metallacycles. [26,27] Choosing between the Hückel and Möbius-type conjugation is not straightforward because of the properties of the d orbitals, which contribute to the macrocyclic conjugation in 5 and 6. [27,28] Porphyrins and porphyrinoids provide a uniquely versatile platform for exploration of macrocyclic p aromaticity.…”
Section: Methodsmentioning
confidence: 99%
“…[26,27] Choosing between the Hückel and Möbius-type conjugation is not straightforward because of the properties of the d orbitals, which contribute to the macrocyclic conjugation in 5 and 6. [27,28] Porphyrins and porphyrinoids provide a uniquely versatile platform for exploration of macrocyclic p aromaticity. pelectron conjugation in porphyrin analogues depends on the topology of the molecular framework, conformation of the macrocycle, tautomerism, and metal coordination.…”
Section: Methodsmentioning
confidence: 99%