Titanium and zirconium compounds stabilized by coordination of heteroscorpionate [N,N,O]-donor ligands. Synthesis, characterization and polymerization activity

Alesso, Giuseppe Andrea; Tabernero, Vanessa; Cuenca, Tomás

doi:10.1016/j.jorganchem.2012.07.004

Cited by 12 publications

(6 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…13 C{ 1 H} NMR (101 MHz, CDCl 3 ): δ 153.1, 148.0, 145.5, 111.5, 14.1, 13.2. Our 1 H and 13 C NMR are consistent with those reported for this compound …”

Section: Methodssupporting

confidence: 91%

“…13 C{ 1 H} NMR (100 MHz, DMSO- d 6 ): δ 154.5, 146.3, 139.4, 129.7, 128.7, 122.8, 118.7, 115.1, 106.1, 68.4, 13.5, 10.8. Our 1 H and 13 C NMR are consistent with those reported for this compound …”

Section: Methodssupporting

confidence: 91%

“…Our 1 H and 13 C NMR are consistent with those reported for this compound. 29 Bis(3,5-diethylpyrazol-1-yl)methanone. It was prepared by the general procedure with 3,5-diethylpyrazole (1.16 g, 9.33 mmol, 6 equiv), triethylamine (1.41 mL, 10.1 mmol, 6.5 equiv), triphosgene (0.460 g, 1.55 mmol, 1.0 equiv), and THF (50 mL).…”

Section: ■ Conclusionmentioning

confidence: 99%

“…Our 1 H and 13 C NMR are consistent with those reported for this compound. 29 2-Bis(pyrazol-1-yl)methylphenol (Table 2, Entry 1). The product was prepared according to the general procedure with salicylaldehyde (0.104 mL, 1.00 mmol, 1.0 equiv), bis(pyrazol-1-yl)methanone (162 mg, 1.00 mmol, 1.0 equiv), DBU (15.2 μL, 0.100 mmol, 0.1 equiv), and THF (3 mL).…”

Section: ■ Conclusionmentioning

confidence: 99%

See 3 more Smart Citations

Metal-free, Mild, and Selective Synthesis of Bis(pyrazolyl)alkanes by Nucleophile-Catalyzed Condensation

Tansky

Comito

2020

J. Org. Chem.

View full text Add to dashboard Cite

Bis(pyrazolyl)alkanes are a prolific class of ligands for catalysis, accessible by the condensation between bis(pyrazolyl)methanones and carbonyls. In this report, we describe a nucleophile-catalyzed innovation on this condensation that avoids the transition metals, high temperatures, reagent excess, and air-sensitive reagents common among the existing protocols. Significantly, this method accommodates sterically hindered and electronically diverse pyrazoles and aldehydes, applicable for systematic ligand optimization. Furthermore, our scope includes azoles and bridging functional groups previously unreported for this reaction, promising for new heteroscorpionate catalysts. We provide the first direct evidence for an elusive reaction intermediate and characterize the most complete mechanism for this condensation.

show abstract

“…13 C{ 1 H} NMR (101 MHz, CDCl 3 ): δ 153.1, 148.0, 145.5, 111.5, 14.1, 13.2. Our 1 H and 13 C NMR are consistent with those reported for this compound …”

Section: Methodssupporting

confidence: 91%

Section: Methodssupporting

confidence: 91%

Section: ■ Conclusionmentioning

confidence: 99%

Section: ■ Conclusionmentioning

confidence: 99%

See 2 more Smart Citations

Metal-free, Mild, and Selective Synthesis of Bis(pyrazolyl)alkanes by Nucleophile-Catalyzed Condensation

Tansky

Comito

2020

J. Org. Chem.

View full text Add to dashboard Cite

show abstract

“…The antifungal properties of several bis(1H-pyrazol-1-yl)methanes (19,(123)(124)(125)(126)(127)(128)(129)(130)(131)(132) have been reported [91]. The moderate properties of 2 and 3 as carbonic anhydrase activators have been described [269].…”

Section: Properties Other Than Complexesmentioning

confidence: 99%

The organic chemistry of poly(1H-pyrazol-1-yl)methanes

Alkorta

Claramunt

Dı́ez-Barra

et al. 2017

Coordination Chemistry Reviews

View full text Add to dashboard Cite

Since their first synthesis by Hückel (1937) and the first systematic exploration by Trofimenko (1970), interest in poly(1H-pyrazol-1-yl)methanes (bis, tris and tetrakis) has increased dramatically. This review focuses on the synthesis and reactivity of these ligands and contains 541 different structures and 271 references. After a brief historical introduction, the synthesis, reactivity, and nature of the coordinated metals are described along with some properties of these compounds, particularly the complete set of X-ray molecular structures. All of the formulae are represented to show the extraordinary richness of poly(1H-pyrazol-1-yl)methanes and to promote the use of the already known poly(1H-pyrazol-1-yl)methanes in coordination chemistry and the design of new ligands with the reported procedures. Keywords Pyrazoles Pyrazolylmethanes bis(1H-pyrazol-1-yl)methanes tris(1H-pyrazol-1yl)methanes tetrakis(1H-pyrazol-1-yl)methanes Metal ligands X-ray structures

show abstract

Natural Amino Acid L‐Phenylalanine Coordinated Zirconocene Complex as Bifunctional Catalyst for the Synthesis of 1,5‐Benzothiazepines

et al. 2022

View full text Add to dashboard Cite

Taken the synthesis of 1,5‐benzothiazepines via the condensation between o‐aminothiophenol with ynones as a paradigm, novel mode of IVB metal based bifunctional catalysis in Lewis acidic‐Brønsted basic (LA‐BB) mode, as well as the effective evidence for how the two catalytic sites interact with substrates has been realized and provided respectively. Specifically, the bifunctional catalyst Cp2Zr[OCOCH(NH2)CH2C6H5]2 was formed through in situ coordination between Cp2ZrCl2 and natural amino acid L‐phenylalanine, which was elucidated by 1H NMR experiment and ESI‐MS analysis. Further control experiment reveals that the excellent catalytic efficiency can attribute to coexistence of Zr (IV) center and Brønsted basic NH2 group contained amino acid ligand. More importantly, with the aid of in situ ESI‐MS, the first catalyst‐substrate adduct for IVB metallocene (IV) catalyst was detected, indicating the Lewis acidic catalytic mode of Zr (IV) center on O atom of ynone. Meanwhile, DFT studies indicated that the true catalytic species presumably be zirconocene (IV) bearing both a bidentate and mono‐dentate carboxylate ligand.

show abstract

Titanium and zirconium compounds stabilized by coordination of heteroscorpionate [N,N,O]-donor ligands. Synthesis, characterization and polymerization activity

Cited by 12 publications

References 55 publications

Metal-free, Mild, and Selective Synthesis of Bis(pyrazolyl)alkanes by Nucleophile-Catalyzed Condensation

Metal-free, Mild, and Selective Synthesis of Bis(pyrazolyl)alkanes by Nucleophile-Catalyzed Condensation

The organic chemistry of poly(1H-pyrazol-1-yl)methanes

Natural Amino Acid L‐Phenylalanine Coordinated Zirconocene Complex as Bifunctional Catalyst for the Synthesis of 1,5‐Benzothiazepines

Contact Info

Product

Resources

About