Rhodapentalenes: Pincer Complexes with Internal Aromaticity

Zhuo, Qingde; Zhang, Hong; Ding, Linting; Lin, Jie; Zhou, Xiaoxi; Hua, Yuhui; Zhu, Jun; Xia, Haiping

doi:10.1016/j.isci.2019.08.027

Cited by 13 publications

(10 citation statements)

References 75 publications

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“…When the starting metal precursor in Scheme 129 was switched to RhCl(PPh 3 ) 3 , rhodapentalenes rather than rhodapentalynes were provided (Scheme 130). 395 Reactions of triynes with RhCl(PPh 3 ) 3 in the presence of PPh 3 and HBF 4 gave 401 and 402. During the preparation of 401, if HBF 4 was not added, intermediate 400 could be isolated.…”

Section: Synthesis Of Metallapentalenes and Metallapentalynesmentioning

confidence: 99%

Metallaaromatic Chemistry: History and Development

2020

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Since the prediction of the existence of metallabenzenes in 1979, metallaaromatic chemistry has developed rapidly, due to its importance in both experimental and theoretical fields. Now six major types of metallaromatic compounds, metallabenzenes, metallabenzynes, heterometallaaromatics, dianion metalloles, metallapentalenes and metallapentalynes (also termed carbolongs), and spiro metalloles, have been reported and extensively studied. Their parent organic analogues may be aromatic, non-aromatic, or even anti-aromatic. These unique systems not only enrich the large family of aromatics, but they also broaden our understanding and extend the concept of aromaticity. This review provides a comprehensive overview of metallaaromatic chemistry. We have focused on not only the six major classes of metallaaromatics, including the main-group-metal-based metallaaromatics, but also other types, such as metallacyclobutadienes and metallacyclopropenes. The structures, synthetic methods, and reactivities are described, their applications are covered, and the challenges and future prospects of the area are discussed. The criteria commonly used to judge the aromaticity of metallaaromatics are presented.

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Section: Synthesis Of Metallapentalenes and Metallapentalynesmentioning

confidence: 99%

Metallaaromatic Chemistry: History and Development

2020

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“…Organometallic materials whose electronic properties could be regulated by altering core metals and chelating ligands offer the potential to modulate the interfaces of photovoltaic devices. Carbolong complexes with strong metal–carbon bonds, which are formed by the chelation of a carbon chain (carbolong ligand) with a transition metal fragment, are a burgeoning class of π-conjugating organometallic frameworks. − Carbolong-derived complexes have emerged as promising materials in many applications due to their excellent photophysical properties. , Recently, an osmium–carbolong complex has been successfully used as an ETL material in OSCs, which had a PCE up to 16.28% …”

Section: Introductionmentioning

confidence: 99%

Tuning an Electrode Work Function Using Organometallic Complexes in Inverted Perovskite Solar Cells

et al. 2021

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Low-work-function (WF) metals (including silver (Ag), aluminum (Al), and copper (Cu)) used as external cathodes in inverted perovskite solar cells (PSCs) encounter oxidation caused by air exposure and halogen-diffusion-induced corrosion, which threaten the long-term stability of the device. The cathode interlayer (CIL) has shown promise in reducing the metal WF and thus boosting the device power conversion efficiency (PCE). However, it remains a challenge for current CIL materials to enable high-WF metals (e.g., Au) to be used as cathodes to achieve PSCs with a superior PCE and long-term stability. Here, we use a series of synthesized (carbolong-derived) organometallic complexes as CILs to tune the electrode WF in inverted PSCs. Density functional theory calculations and surface characterizations show that the organometallic complexes that contain anions and cations are prone to form anion−cation dipoles on the metal surface, hence drastically reducing the metal's WF. Photovoltaic devices based on a Ag cathode, which was modified with these organometallic complexes, received a boosted PCE up to 21.29% and a remarkable fill factor that reached 83.52%, which are attributed to the dipole-enhanced carrier transport. The environmental stability of PSCs was further improved after employing Au as a cathode with these organometallic complexes, and the modified devices exhibited no efficiency loss after 4080 h storage measurements.

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“…As the relative reactivity and stability of the metal-oxygen species are highly dependent on the supporting ligands or coordination environments ( Cook and Borovik, 2015 ; Kovacs, 2015 ; Neu et al., 2015 ; Yan Poon et al., 2019 ), the rational ligand design constitutes a promising way to tune the relative stability and reactivity of metal-peroxo complexes ( Mirica et al., 2004 ; Baglia et al., 2017 ). Internally aromatic metallacycles, featured by a rigid CˆCˆC-tridentate framework with electronically delocalized metallacyclic cores ( Zhuo et al., 2019 ), were demonstrated to be efficient in stabilizing various metallacycle derivatives ( Zhu et al., 2015 ). Structurally, these derivatives are termed as “carbolong complexes,” due to their unique ring systems consisting of different number of carbon atoms and one metal center in the equatorial plane ( Zhu and Xia, 2018 ).…”

Section: Introductionmentioning

confidence: 99%

Dioxygen Activation by Internally Aromatic Metallacycle: Crystallographic Structure and Mechanistic Investigations

Deng

Cai

et al. 2020

iScience

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Summary Mononuclear metal-peroxo species are invoked as the key intermediates in metalloenzymatic or synthetic catalysis. However, either transience or sluggishness reactivity of synthetic analogs of metal-peroxo species impedes our understanding of oxygen activation mechanism. Herein, we designed and characterized a dioxygen-derived mononuclear osmium-peroxo complex, in which the peroxo ligand is stabilized by internally aromatic metallacycle. We demonstrate that the osmium-peroxo species shows catalytic activity toward promoterless alcohol dehydrogenations. Furthermore, computational studies provide a new mechanism for the osmium-peroxo-mediated alcohol oxidation, starting with the concerted double-hydrogen transfer and followed by the generation of osmium-oxo species. Interestingly, the internally aromatic metallacycle also plays a vital role in catalysis, which mediates the hydrogen transfer from osmium center to the distal oxygen atom of Os–OOH moiety, thus facilitating the Os–OOH→Os=O conversion. We expect that these insights will advance the development of aromatic metallacycle toward aerobic oxidation catalysis.

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Rhodapentalenes: Pincer Complexes with Internal Aromaticity

Abstract: A concept for pincer chemistry: internal aromaticity involving metal d-orbitals Stable cyclic rhodium complexes with obvious rhodium carbene character Dual stabilization of rigid CCC pincer architectures and intrinsic aromaticity Rhodium-containing aromatics with a single metal entity

Cited by 13 publications

References 75 publications

Metallaaromatic Chemistry: History and Development

Metallaaromatic Chemistry: History and Development

Tuning an Electrode Work Function Using Organometallic Complexes in Inverted Perovskite Solar Cells

Dioxygen Activation by Internally Aromatic Metallacycle: Crystallographic Structure and Mechanistic Investigations

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