Osmapentalenofurans Constructed by Reacting Os≡C1 of Osmapentalyne with Phenols DOI Open Access
Xiaofei Yang, Kunming Zhang,

Yuteng Zhang

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(68)

Published: Aug. 23, 2024

Abstract Over the past decade, significant research efforts have focused on osmapentalyne, characterized by more reactive Os≡C7 (Carbon atoms numbered in a clockwise direction osmapentalyne skeleton), across areas encompassing electrophilic, nucleophilic, and addition reactions. Nevertheless, reactivity of featuring Os≡C1 remains ripe for further exploration. In this investigation, we effectively synthesized lineage osmapentalenofurans through nucleophilic reaction incorporating with phenols. These resulting complexes demonstrate near‐infrared luminescence traits both solid liquid states. Particularly noteworthy is osmapentalenofuran derived from tetraphenylethane (TPE) unit, which showcases remarkable aggregation‐induced emission (AIE) property aggregated state. are also able to extend their range reactions, including reactions base isonitrile. This study not only broadens scope applications metal aromatics but furnishes valuable insights into realm specialized functional materials.

Language: Английский

Enhancing Precatalyst Performance and Robustness through Aromaticity: Insights from Iridaheteroaromatics DOI

Sandip Bapu Khatal,

Siddhartha K. Purkayastha, Ankur K. Guha

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(4), P. 2480 - 2493

Published: Feb. 3, 2024

Despite the inherent stability-enhancing benefits of dπ–pπ conjugation-induced aromaticity, metallaaromatic catalysts remain underutilized in this context, despite their reactivity with organic functionalities stoichiometric reactions. We present a strategy for synthesizing diverse range iridaheteroaromatics, (L^L)IrIII(Cp*)I, including iridapyridylidene-indole, iridapyridene-indole, and iridaimidazole, via situ deprotonation/metalation reactions utilizing [Cp*IrCl2]2 respective ligands. These exhibit enhanced σ-donor π-acceptor properties, intrinsic σ–π continuum attributes, versatile binding sites, contributing to stability through aromaticity. Spectroscopic data, X-ray crystallographic density functional theory calculations confirm iridaheteroaromatics formidable catalytic ability across spectrum transformations under industrially viable conditions, notably excelling highly selective cross alkylation β-alkylation alcohols an eco-friendly avenue quinolone synthesis, achieving remarkably high turnover frequencies (TOFs). Additionally, method extends self-condensation bioalcohols like ethanol, n-butanol, n-hexanol water, replicating conditions frequently encountered primary fermentation solutions. strong activity fast reaction rates, TOFs, broad substrate compatibility, remarkable selectivity, displaying potential as robust large-scale applications emphasizing practical significance beyond structural theoretical importance.

Language: Английский

Citations

2
Synthesis and Structure of Chlororuthenacyclopentatriene DOI

Zhenwei Chu,

Zhishun Peng,

Xu Cheng

et al.

Inorganic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(23), P. 8479 - 8488

Published: Jan. 1, 2024

Chlororuthenacyclopentatriene, representing a new member of the ruthenaaromatic family, was successfully prepared using reactions RuCl 2 (PPh 3 ) with o -phenyldiyne derivatives in presence excess HCl.

Language: Английский

Citations

1
Preparation, Aromaticity, and Bromination of Spiro Iridafurans DOI
Miguel A. Esteruelas, Félix León,

Sonia Moreno-Blázquez

et al.

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(41), P. 16810 - 16824

Published: Oct. 2, 2023

Iridium centers of [Ir(μ-Cl)(C8H14)2]2 (1) activate the Cβ(sp2)-H bond benzylideneacetone to give [Ir(μ-Cl){κ2-C,O-[C(Ph)CHC(Me)O]}2]2 (2), which is starting point for preparation spiro iridafurans IrCl{κ2-C,O-[C(Ph)CHC(Me)O]}2(PiPr3) (3), [Ir{κ2-C,O-[C(Ph)CHC(Me)O]}2(MeCN)2]BF4 (4), [Ir(μ-OH){κ2-C,O-[C(Ph)CHC(Me)O]}2]2 (5), Ir{κ2-C,O-[C(Ph)CHC(Me)O]}2{κ2-C,N-[C6MeH3-py]} (6), and Ir{κ2-C,O-[C(Ph)CHC(Me)O]}2{κ2-O,O-[acac]} (7). The five-membered rings are orthogonally arranged with oxygen atoms in trans an octahedral environment iridium atom. Spiro aromatic. degree aromaticity negative charge CH-carbon depend on ligand carbon directly attached metal. Aromaticity has been experimentally confirmed by bromination N-bromosuccinimide (NBS). Reactions sensitive ring attacked CH-carbon. Iridafurans can be selectively brominated, when different ligands lie metalated carbons. Bromination 3 occurs chloride, whereas 6 takes place pyridyl. first gives IrCl{κ2-C,O-[C(Ph)CBrC(Me)O]}{κ2-C,O-[C(Ph)CHC(Me)O]}(PiPr3) (8), reacts more NBS form IrCl{κ2-C,O-[C(Ph)CBrC(Me)O]}2(PiPr3) (9). second yields Ir{κ2-C,O-[C(Ph)CBrC(Me)O]}{κ2-C,O-[C(Ph)CHC(Me)O]}{κ2-C,N-[C6MeH3-py]} (10). origin selectivity kinetic, rate-determining step reaction being attack. activation energy depends atom; a higher allows lower energy. Accordingly, complex 7 undergoes acetylacetonate ligand, giving Ir{κ2-C,O-[C(Ph)CHC(Me)O]}2{κ2-O,O-[acacBr]} (11).

Language: Английский

Citations

1
Osmapentalenofurans Constructed by Reacting Os≡C1 of Osmapentalyne with Phenols DOI Open Access
Xiaofei Yang, Kunming Zhang,

Yuteng Zhang

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(68)

Published: Aug. 23, 2024

Abstract Over the past decade, significant research efforts have focused on osmapentalyne, characterized by more reactive Os≡C7 (Carbon atoms numbered in a clockwise direction osmapentalyne skeleton), across areas encompassing electrophilic, nucleophilic, and addition reactions. Nevertheless, reactivity of featuring Os≡C1 remains ripe for further exploration. In this investigation, we effectively synthesized lineage osmapentalenofurans through nucleophilic reaction incorporating with phenols. These resulting complexes demonstrate near‐infrared luminescence traits both solid liquid states. Particularly noteworthy is osmapentalenofuran derived from tetraphenylethane (TPE) unit, which showcases remarkable aggregation‐induced emission (AIE) property aggregated state. are also able to extend their range reactions, including reactions base isonitrile. This study not only broadens scope applications metal aromatics but furnishes valuable insights into realm specialized functional materials.

Language: Английский

Citations

0