Facile synthesis of polycyclic metallaarynes

Ruan, Wenqing; Leung, T. C.; Shi, Chuan; Lee, Kenneth K.; Sung, Herman H. Y.; Williams, Ian D.; Lin, Zhenyang; Jia, Guochen

doi:10.1039/c8sc02086h

Cited by 32 publications

(23 citation statements)

References 39 publications

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“…To obtain cyclobutaosmapentalenes with more conjugated groups attached to its metallacyclic moiety, we have developed a new synthetic method based on the one-pot "carbolong" method involving a new multiyne. Thus, treatment of OsCl 2 (PPh 3 ) 3 (4) with the multiyne 5 and PPh 3 in dichloromethane under argon at 55 ℃ for 6 h afforded an air stable complex (6) containing a conjugated 3-thiophenyl group in 80% yield (Scheme 1). Complex 6 was identified by its nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HRMS) data.…”

Section: Synthesis Of New Carbolong Complexesmentioning

confidence: 99%

Carbolong Complexes as Photothermal Materials

Wu¹,

Huang²,

Zhuo³

et al. 2019

Chin. J. Org. Chem.

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A series of photothermal cyclobutaosmapentalenes with conjugated groups attached to the metallacycle were synthesized from the reaction of OsCl 2 (PPh 3) 3 with an organic multiyne and PPh 3 , followed by a [2＋2] cycloaddition with terminal alkynes. These highly conjugated metallacycles showed broad UV-Vis absorption and good photothermal efficiency. These easily synthesized metallacycles represent a type of new photothermal material. Keywords organometallics; metallacycle; photothermal Metallacycles [1～5] containing a metal and a conjugated carbon-chain have attracted more and more attention as novel materials, because they could show both properties of the metal fragment and the organic framework. For instance, a series of planar Craig-type Möbius [6] metallacylces, called "carbolong" complexes, [6s～6t,7] have been reported. These "carbolong" complexes displayed various properties, including aggregation enhanced emission (AEE), [8] single-molecular conductivity, [9] photothermal conversion, [10] and photoacoustic response. [10a] Among these interesting properties, the photothermal conversion is one of the most important properties for carbolong complexes. For example, the photothermal efficiency of complex 1 (Figure 1a) is about equal to the performance of Au nanoparticles, [11] which are normally used for surface or physical modifications. [12] For comparison, complex 1 can be easily chemically modified and bonded to functional frameworks, obtaining functional macromolecules or micelles (Figure 1b). [10b～10d] Interestingly, the substituents in complex 1 have considerable influence on its absorption and photophysical properties. This effect has also been observed in complex 2 (Figure 1a), which shows a broad absorption covering the range of 700～900 nm owing to the J-aggregates in the substituent. [10c] Recently, our group discovered a simple way to prepare "carbolong" complexes in a one-pot reaction [13,14] by treatment of multiyne ("carbolong") with simple organometallic starting material. This one-pot "carbolong" method feasibly offered us a means of introducing more substituent groups into these matallacycles using different

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Section: Synthesis Of New Carbolong Complexesmentioning

confidence: 99%

Carbolong Complexes as Photothermal Materials

Wu¹,

Huang²,

Zhuo³

et al. 2019

Chin. J. Org. Chem.

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“…Cyclic metal carbynes include metallabenzynes, [9] metallanaphthalynes, [10] metallaphenanthrynes, and metallaanthracynes. [11] The earliest reactivity study of cyclic metal carbynes concerned metallabenzynes. Since Jia et al reported the first metallabenzyne (osmabenzyne) in 2001, [12] they have also reported on the chemical reactivities of many other metallabenzynes, and found that they can undergo aromatic electrophilic substitution reactions with a series of electrophiles (H + , NO + , Br + , Cl + ) to form other metallabenzynes and some metallabenzene-like complexes.…”

Section: Introductionmentioning

confidence: 99%

“…[4a,10,17] In 2018, Jia's group successfully prepared the first examples of β-metallanaphthalyne, metallaanthracyne, and metallaphenanthryne complexes. [11] We have also synthesized a series of osmanaphthalynes and the first examples of αosmaanthracyne and α-osmaphenanthryne species by means of visible-light-induced intramolecular cyclization reactions. [4a] Nevertheless, research on the reactivity of metallanaphthalynes in comparison to that of metallabenzynes is extremely rare.…”

Section: Introductionmentioning

confidence: 99%

“…Cyclic metal carbynes include metallabenzynes, [9] metallanaphthalynes, [10] metallaphenanthrynes, and metallaanthracynes [11] . The earliest reactivity study of cyclic metal carbynes concerned metallabenzynes.…”

Section: Introductionmentioning

confidence: 99%

“…Metallanaphthalynes are a class of fused ring metallacyclic complexes that are still relatively rare among cyclic metal carbynes, although they have been discussed in our previous articles [4a,10,17] . In 2018, Jia's group successfully prepared the first examples of β‐metallanaphthalyne, metallaanthracyne, and metallaphenanthryne complexes [11] . We have also synthesized a series of osmanaphthalynes and the first examples of α‐osmaanthracyne and α‐osmaphenanthryne species by means of visible‐light‐induced intramolecular cyclization reactions [4a] .…”

Section: Introductionmentioning

confidence: 99%

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Nucleophilic Reactions of Osmanaphthalynes with PMe₃ and H₂O

Zhang

Lin

Yang

et al. 2021

Chemistry A European J

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Members of a new class of complexes, 2(CF 3 ), 2(H), 2(Br), 2(I), and 2(OCH 3 ), have been synthesized in a one-pot method involving the treatment of osmanaphthalynes bearing corresponding substituents (1(CF 3 ), 1(H), 1(Br), 1(I), and 1(OCH 3 )) with trimethylphosphine (PMe 3 ) and water. The main reaction process involves two steps, namely a ligandexchange with trimethylphosphine and nucleophilic addition of water to the Os�C bond of the osmanaphthalyne. The substituents have a significant influence on the rate of the reaction, as befits a nucleophilic addition. Fortunately, the key intermediate [1(OCH 3 )]' could be successfully captured, and the detailed reaction mechanism has been explored with the aid of density functional theory (DFT) calculations, which were in excellent agreement with the experimental findings. All of the target complexes have been fully characterized by 1 H, 31 P{ 1 H}, and 13 C{ 1 H} NMR spectroscopy, high-resolution mass spectrometry, and elemental analysis.

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

Chu

Cheng

et al. 2019

Angewandte Chemie

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Metalla‐aromatics are important complexes that show unique properties owing to their highly conjugated systems, which show Hückel or Möbius aromaticity. Recently, several metalla‐aromatics showing spiro‐aromaticity or σ‐aromaticity have been reported. Herein, we report the isolation of the first cyclopropametallanaphthalenes, in which the metallacyclopropene ring shows σ‐aromaticity and weak hyperconjugative aromaticity. The reaction of OsCl2(PPh3)3 with o‐ethynylphenyl alkynes in the presence of PPh3 followed by protonation with HCl yielded the first cyclopropametallanaphthalenes. The reaction mechanism and the aromaticity were also investigated by density functional theory studies.

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Facile synthesis of polycyclic metallaarynes

Abstract: The preparation and structural characterization of the first examples of a β-metallanaphthalyne and tricyclic metallaarynes are described.

Cited by 32 publications

References 39 publications

Carbolong Complexes as Photothermal Materials

Carbolong Complexes as Photothermal Materials

Nucleophilic Reactions of Osmanaphthalynes with PMe₃ and H₂O

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

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Facile synthesis of polycyclic metallaarynes

Abstract: The preparation and structural characterization of the first examples of a β-metallanaphthalyne and tricyclic metallaarynes are described.

Cited by 32 publications

References 39 publications

Carbolong Complexes as Photothermal Materials

Carbolong Complexes as Photothermal Materials

Nucleophilic Reactions of Osmanaphthalynes with PMe3 and H2O

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

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Nucleophilic Reactions of Osmanaphthalynes with PMe₃ and H₂O