The aromatic dianion metalloles

Wei, Junnian; Zhang, Wen‐Xiong; Xi, Zhenfeng

doi:10.1039/c7sc04454b

Cited by 108 publications

(75 citation statements)

References 69 publications

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“…[10] As shown in Figure 4, the HOMO of 1a essentially consists of the lone pair of the two terminal carbon anions,which can donate the electron into the metal center in a s-fashion. [4,12] Upon reduction the central CÀCb ond get shortened, whereas the two terminal CÀCbonds become elongated. [11] Hence,d ilithio reagents can exhibit different valence states (A, B and C)i nt ransition metal complexes (Scheme 3), which has also been demonstrated in our previous work.…”

Section: Aromaticity and Dft Analysismentioning

confidence: 99%

Tetralithio Metalla‐aromatics with Two Independent Perpendicular Dilithio Aromatic Rings Spiro‐fused by One Manganese Atom

et al. 2019

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Herein, we present the realization of ac lass of unprecedented aromatic structures 2:m etalla-aromatics with two independent and perpendicular aromatic rings spiro-fused by atransition-metal spiro atom, of which their corresponding organic analogues are impossible.T etralithio spiro manganacycles 2 are readily synthesized from 1,4-dilithio-1,3-butadienes 1 and MnCl 2 in the presence of lithium. The aromaticity of 2 is supported by experimental measurements (X-ray structural analysis,N MR) and theoretical analyses (NICS, ACID,M Os). The spiro atom Mn in 2 uses its 3d xz and 3d xy orbitals to form the two perpendicular manganacycles,w hich are two independent 6p aromatic systems.Theoretical analyses reveal that the Li cations play an indispensable role in governing their geometric and electronic structures and hence their aromaticity.T herefore,t his work contributes not only to enrich the concept of aromaticity,b ut also to deepen the understanding of the fundamental chemical bonding. Scheme 1. Classes of spiro metalla-aromatics.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under https://doi.

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Section: Aromaticity and Dft Analysismentioning

confidence: 99%

Tetralithio Metalla‐aromatics with Two Independent Perpendicular Dilithio Aromatic Rings Spiro‐fused by One Manganese Atom

et al. 2019

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“…(8) (7); C1-In1-C4 75.75 (11), C2-C1-In1 113.9(2), C1-C2-C31 18.4 (3), C2-C3-C4 117.9(3), C3-C4-In1114.0(2). (7), In1ÀLi2 2.654(6), In2ÀLi3 2.647 (7), In2ÀLi4 2.641(6);C1-In1-C4 80.93 (12), C2-C1-In1 111.0(2), C1-C2-C3 118.9(3), C2-C3-C4 118.8 (3), C3-C4-In1 110.3(2), C5-In2-C8 80.75 (14),C 6-C5-In2 111.0(2), C5-C6-C71 18.9(3), C6-C7-C8 118.8 (3), C7-C8-In2 110.6(3).…”

Section: Resultsunclassified

“…We have been interested in the synthesis and structures of metallacyclopentadienes and aromatic dianion metalloles . As part of our continued interest in these types of organometallic compounds, we have investigated the synthesis of metallacyclopentadienes and metalloaromatics of indium.…”

Section: Introductionmentioning

confidence: 99%

“…We have been interested in the synthesis and structures of metallacyclopentadienes [1b, 13] anda romaticd ianion metalloles. [14,15] As part of our continued interesti nt hese types of organometallic compounds, we have investigated the synthesis of metallacyclopentadienes and metalloaromatics of indium. In this paper,w ereport the first synthesis and structural analysisofaseries of metallacycleso fi ndium (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

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Indacyclopentadienes and Aromatic Indacyclopentadienyl Dianions: Synthesis and Characterization

Zhang

Yang

Zhang

et al. 2019

Chemistry A European J

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A series of unprecedented metallacycles of indium, including indacyclopentadienes (2), spiro indacyclopentadienes (3), aromatic indacyclopentadienyl dianions with an In−Li bond (4), and aromatic indacyclopentadienyl dianions with an In−In bond (5), were synthesized and structurally characterized by single‐crystal X‐ray structural analysis for the first time. Both indacyclopentadienes 2 and 3 were synthesized by reaction of 1,4‐dilithio‐1,3‐butadienes with InCl3. Structural transformations between 2 and 3 were observed. Reduction of indacyclopentadienes 2 with an excess amount of lithium afforded aromatic indacyclopentadienyl dianions 4 with an In−Li bond or 5 with an In−In bond, respectively, depending on the substituents on the ring. The aromatic character of 4 and 5 was confirmed by both experimental measurements and theoretical analysis.

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“…Metalla-aromatics [1] are very interesting species and can be used as valuable materials owing to their high stability and unique properties.E arly metalla-aromatics such as metallabenzene [2,3] and metallabenzyne [4,5] are Hückel aromatics. Recently,m etallacycles that show Mçbius aromaticity, [6,7] spiro-aromaticity, [8] or s-aromaticity [9] have also been demonstrated. However,m etallacycles that show s-aromaticity arising from the delocalization of s-bonds are rare.Only two examples containing afused s-aromatic metallacyclopropene unit have been reported:c yclopropaosmapentalene (I,F igure 1) [9a] and cyclopropaosmafuran (II,F igure 1).…”

mentioning

confidence: 99%

Synthesis and Characterization of Cyclopropaosmanaphthalenes Containing a Fused σ‐Aromatic Metallacyclopropene Unit

Chu

Cheng

et al. 2019

Angew Chem Int Ed

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Metalla-aromatics are important complexes that show unique properties owing to their highly conjugated systems,which show Hückel or Mçbius aromaticity.Recently, several metalla-aromatics showing spiro-aromaticity or saromaticity have been reported. Herein, we report the isolation of the first cyclopropametallanaphthalenes,i nw hich the metallacyclopropene ring shows s-aromaticity and weak hyperconjugative aromaticity.T he reaction of OsCl 2 (PPh 3 ) 3 with o-ethynylphenyl alkynes in the presence of PPh 3 followed by protonation with HCl yielded the first cyclopropametallanaphthalenes.T he reaction mechanism and the aromaticity were also investigated by density functional theory studies.

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The aromatic dianion metalloles

Abstract: This perspective includes the synthesis and future challenges of aromatic dianion metalloles and their analogues.

Cited by 108 publications

References 69 publications

Tetralithio Metalla‐aromatics with Two Independent Perpendicular Dilithio Aromatic Rings Spiro‐fused by One Manganese Atom

Tetralithio Metalla‐aromatics with Two Independent Perpendicular Dilithio Aromatic Rings Spiro‐fused by One Manganese Atom

Indacyclopentadienes and Aromatic Indacyclopentadienyl Dianions: Synthesis and Characterization

Synthesis and Characterization of Cyclopropaosmanaphthalenes Containing a Fused σ‐Aromatic Metallacyclopropene Unit

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