Ruthenium Complexes with an Anthyridine‐based Ligand. Synthesis, Characterization and Catalytic Activity

Lo, Yih‐Hsing; Liu, Yi Hung; Peng, Shie‐Ming; Liu, Shiuh‐Tzung

doi:10.1002/jccs.201300084

Cited by 9 publications

(7 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The mechanistic study indicates that the cooperation of the two palladium centers, which are separated by 3.1696(7) Å, is responsible for the highly activity of the catalyst. We have also synthesized another ligand 5-phenyl-2,8-bis(6′-bipyridinyl)-1,9,10-anthyridine ( L , Scheme ), which is capable of accommodating two metal ions . Coordination of this ligand with metal ions afforded a set of dimetallic complexes including ruthenium(II), nickel(II), and copper(II), in which the distances between the metal ions are ca.…”

Section: Introductionmentioning

confidence: 92%

See 1 more Smart Citation

Tetra- and Dinuclear Palladium Complexes Based on a Ligand of 2,8-Di-2-pyridinylanthyridine: Preparation, Characterization, and Catalytic Activity

Lin

Liu

et al. 2021

Organometallics

View full text Add to dashboard Cite

Complexation of L [L = 5-phenyl-2,8-di-2-pyridinyl-anthyridine] with [Pd(CH 3 CN) 4 ](BF 4 ) 2 and [Pd(CH 3 CN) 3 Cl](BF 4 ) in a molar ratio of 1:2 rendered the corresponding dinuclear complexes [Pd 2 L (CH 3 CN) 4 ](BF 4 ) 4 (1) and [Pd 2 L (CH 3 CN) 2 Cl 2 ](BF 4 ) 2 ( 2), respectively. However, treatment of L with (COD)PdCl 2 followed by anion exchange yielded a tetranuclear complex [Pd 4 L 3 Cl 4 ](PF 6 ) 4 (4a). Structures of these complexes are characterized by both spectroscopy and X-ray crystallography. Interconversion of these three complexes was studied via the manipulation of stoichiometric ratio of ligand to metal precursor. The catalytic activity of these complexes for carbonylative Suzuki− Miyaura cross-coupling was investigated. Complex 2 shows an excellent catalytic activity on the reaction of aryl iodide with arylboronic acid in the presence of atmospheric pressure of CO to give the corresponding benzophenones.

show abstract

Section: Introductionmentioning

confidence: 92%

“…Coordination of this ligand with metal ions afforded a set of dimetallic complexes including ruthenium(II), nickel(II), and copper(II), in which the distances between the metal ions are ca. 5 Å . We are also delighted to learn that these dinuclear metal complexes show a possible synergistic effect in various catalytic reactions .…”

Section: Introductionmentioning

confidence: 99%

Tetra- and Dinuclear Palladium Complexes Based on a Ligand of 2,8-Di-2-pyridinylanthyridine: Preparation, Characterization, and Catalytic Activity

Lin

Liu

et al. 2021

Organometallics

View full text Add to dashboard Cite

show abstract

“…5-Phenyl-2,8-bis(2-pyridinyl)anthyridine ( L ) is a pentanitrogen donor system, containing two bipyridinyl moieties that are suitable for the construction of bimetallic systems via bis-chelation or ortho cyclometalation (Scheme , I and II ). Indeed, the related dimetallic complexes have been disclosed in our previous works. , Interestingly, the reaction of L with (COD)PdCl 2 followed by anion exchange yielded the tetranuclear complex Pd 4 L 3 , in which one ligand L acts a monodentate ligand with four nitrogen donors bound to four different palladium centers (denoted in red in Pd 4 L 3 , Scheme ). Nevertheless, in all these cases, the nitrogen atom (N (10) ) at the 10-position of the anthyridine remains as a free site.…”

Section: Introductionmentioning

confidence: 97%

An Anthyridine-Based Pentanitrogen Donor Switches from Mono- to Tetradentate with Pd(II) Ions

Liu

Peng

et al. 2021

Organometallics

View full text Add to dashboard Cite

Treatment of 5-phenyl-2,8-bis(2-pyridinyl)anthyridine (L) with (PPh 3 ) 2 PdCl 2 or (dppe)PdCl 2 in the presence of a silver salt resulted in the formation of [trans-(PPh 3 ) 2 PdLCl](BF 4 ) (1a), [trans-(PPh 3 ) 2 PdL(MeCN)]-(BF 4 ) 2 (1b), [trans-(PPh 3 ) 2 PdLCl](PF 6 ) (1c) ,or [cis-(dppe)PdLCl](BF 4 ) (4), respectively. The ligand L in these complexes acts as a monodentate ligand with N (10) of anthyridine binding to the metal center. In the presence of PPh 3 , dinuclear complexes [Pd 2 L(CH 3 CN) 2 Cl 2 ](BF 4 ) 2 (2) and [Pd 2 L(CH 3 CN) 4 ]-(BF 4 ) 4 (3) readily underwent dechelation to yield 1a,b, respectively, whereas the reaction of 2 with dppe gave 4. On the other hand, treatment of 1a and 4 with S 8 in the presence of a sufficient amount of palladium ions provided the corresponding dinuclear complex 2. Furthermore, this kind of substitution is also applicable with the Pd-Me complex [Pd 2 L(CH 3 CN) 2 Me 2 ](BF 4 ) 2 ( 5), which could be prepared from complexation of L with 2 equiv of [(COD)Pd(CH 3 CN)Me](BF 4 ). Thus, [trans-(PPh 3 ) 2 PdLMe](BF 4 ) (7) was obtained by the reaction of 5 with PPh 3 . However, the reaction of PPh 3 with [Pd 2 L(CH 3 CN) 2 (MeCO) 2 ](BF 4 ) 2 (6), a CO insertion product of 5, gave a messy result. The catalytic activity of these complexes in the Suzuki−Miyaura coupling of aryl halide with arylboronic acid under a CO atmosphere was investigated. Crystal structures of 1c, 4, 5, and 7 are reported to confirm their structural details. This work demonstrates the novelty of L as a hypodentate ligand toward palladium ions.

show abstract

“…Therefore, α-C-H cyanated amines are valuable synthetic intermediates, for example for the synthesis of α-amino acids. 1,2 One general trend in the α-C-H cyanation of amines is that aniline-type structures appear to be more reactive, [3][4][5][6][7][8][9][10][11][12][13][14][15][16] possibly due to the lower bond dissociation energy of the functionalized α-C-H bond. In comparison, α-C-H cyanations of tertiary amines with unactivated (not benzylic or aniline-type) α-C-H bonds are not as well established.…”

Section: Introductionmentioning

confidence: 99%

Iron-Catalyzed α-C–H Cyanation of Simple and Complex Tertiary Amines

2021

View full text Add to dashboard Cite

This manuscript details the development of a general and mild protocol for the α-C-H cyanation of tertiary amines as well as its application in late stage functionalization. Suitable substrates include tertiary aliphatic, benzylic, and aniline-type substrates as well as complex substrates. Functional groups tolerated under the reaction conditions include various heterocycles, as well as ketones, amides, olefins, and alkynes. This broad substrate scope is remarkable, as comparable reaction protocols for α-C-H cyanation frequently occur via free radical mechanisms, and are thus fundamentally limited in their functional group tolerance. In contrast, the presented catalyst system tolerates functional groups that typically react with free radicals, suggesting an alternative reaction pathway. All components of the described system are readily available, allowing implementation of the presented methodology without the need for lengthy catalyst synthesis.Recent mechanistic work in the Fe catalyzed α-C-H oxidation of tertiary amines has uncovered a radical rebound ASSOCIATED CONTENT Supporting Information. Reaction optimization details, synthetic procedures, characterization for new and known compounds.

show abstract

Ruthenium Complexes with an Anthyridine‐based Ligand. Synthesis, Characterization and Catalytic Activity

Abstract: Complexation of 2,7-bis(2-pyridinyl)-9-phenylanthyridine (4)

Cited by 9 publications

References 28 publications

Tetra- and Dinuclear Palladium Complexes Based on a Ligand of 2,8-Di-2-pyridinylanthyridine: Preparation, Characterization, and Catalytic Activity

Tetra- and Dinuclear Palladium Complexes Based on a Ligand of 2,8-Di-2-pyridinylanthyridine: Preparation, Characterization, and Catalytic Activity

An Anthyridine-Based Pentanitrogen Donor Switches from Mono- to Tetradentate with Pd(II) Ions

Iron-Catalyzed α-C–H Cyanation of Simple and Complex Tertiary Amines

Contact Info

Product

Resources

About