Synthesis and charactrization palladium polysulfide complexes of N-heterocyclic carbenes

Chen, Chao; Xia, Qinqin; Qiu, Huayu; Chen, Wanzhi

doi:10.1016/j.jorganchem.2013.11.037

Cited by 6 publications

(2 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Moreover, the complex signals do not indicate any intensity loss when referenced to hexamethylbenzene as internal standard (Figure S13). The decrease of catalytic activity of complex 6 in the presence of S 8 has therefore tentatively been attributed to S n coordination to the metal center rather than carbene dissociation and subsequent thione formation . A similar effect of S 8 has been noted also in related ketone hydrosilylation catalysis using the same complex …”

Section: Resultsmentioning

confidence: 97%

Comparing the Activity of N-Heterocyclic Carbene Iron Complexes and Free Carbene Precursors in the Hydrosilylation of CO₂

2023

View full text Add to dashboard Cite

Piano-stool iron complexes with N-heterocyclic carbene (NHC) ligands have shown high potential in the activation and conversion of CO bonds in aldehydes, ketones, and esters. Here we demonstrate the expansion of this activity to the functionalization of CO2 with amines to form N-formamide products in the presence of a silane (PhSiH3). This synthetically valuable utilization of CO2 as C1-synthon is catalyzed by iron complexes containing a variety of different NHC ligands. Structural variations of the NHC ligands did not reveal any correlation with catalytic activity, with imidazole and triazole-derived NHCs reaching similar conversions. However, the use of BF4 – as counterion in cationic complexes, and also incorporating a Cp* instead of a Cp spectator ligand led to a marked decrease in catalytic activity. While NHC iron complexes reach mediocre activity (about 50% conversion at 5% catalyst loading in 24 h), the corresponding imidazolium and triazolium carboxylates as precursors of free carbenes display excellent catalytic activity with essentially full conversion after 1 h at 1 mol % loading. Experiments at variable iron complex loading as well as carbene trapping experiments with S8 together with spectroscopic investigations demonstrated a high stability of the Fe–CNHC bond during catalysis and lend strong support to a NHC iron unit as catalytically active species rather than free NHC resulting from Fe–NHC dissociation, even though free NHCs are excellent catalysts for this reaction. Optimized of reaction conditions, in particular the addition of another equivalent of silane allowed to reach high conversions of piperidine and CO2 to N-formylpiperidine using a triazolylidene iron complex as catalyst precursor.

show abstract

Section: Resultsmentioning

confidence: 97%

Comparing the Activity of N-Heterocyclic Carbene Iron Complexes and Free Carbene Precursors in the Hydrosilylation of CO₂

2023

View full text Add to dashboard Cite

show abstract

“…A structure survey was carried out in the Cambridge Structural Database (CSD version 5.42, update of November 2020; Groom et al, 2016). It revealed 28 hits for dicationic dimers with a Pd 2 S 2 core, of which ten can be compared with the title compound as they feature the sulfur atoms embedded in a chelating ligand [refcodes CUYLIT (Kouno et al, 2015), NORGEG (Albinati et al, 1997), NOXVAZ (Chen et al 2015), POTMUG (Kersting, 1998), QOCCUG (Su et al, 2000), SELGUL (Leung et al, 1998), TEGWUY (Cabeza et al, 2006), TIXLOE (Mane et al, 2019), XAHBUI (Nayan Sharma et al, 2015), XULYUZ (Azizpoor Fard et al, 2015)]. Hinge angles in the range 115.3-156.6 were measured for these compounds, all values higher than that measured for the title compound [108.0 (1) ].…”

Section: Database Surveymentioning

confidence: 99%

Crystal structure of a dicationic Pd^II dimer containing a 2-[(diisopropylphosphanyl)methyl]quinoline-8-thiolate pincer ligand

Clerc¹,

Saffon‐Merceron²,

Monot³

et al. 2022

Acta Cryst E

View full text Add to dashboard Cite

A dicationic PdII dimer, bis{2-[(diisopropylphosphanyl)methyl]quinoline-8-thiolato}palladium(II) bis(hexafluoridoantimonate) dichloromethane monosolvate, [Pd2(C32H42N2P2S2)](SbF6)2·CH2Cl2, containing a 2-[(diisopropylphosphanyl)methyl]quinoline-8-thiolate pincer ligand, was isolated and its crystal structure determined. The title compound crystallizes in the orthorhombic space group Pbca. A dimeric structure is formed by bridging coordination of the S atoms. The geometry of the butterfly-shaped Pd2S2 core is bent, with a hinge angle of 108.0 (1)° and a short Pd...Pd distance of 2.8425 (7) Å. These values are the lowest measured compared to ten dicationic dimers with a Pd2S2 core featuring sulfur atoms embedded in a chelating ligand. One of the two hexafluoridoantimonate anions is disordered over two sets of positions with site-occupancy factors of 0.711 (5) and 0.289 (5). The crystal structure is stabilized by many C—H...F and C—H...π interactions, forming a supramolecular network.

show abstract

Synthesis, Structure, Biological Evaluation, and Catalysis of Two Pyrazole‐Functionalized NHC–Ru^II Complexes

Chen

Zheng

et al. 2017

Eur J Inorg Chem

Self Cite

View full text Add to dashboard Cite

Two ruthenium complexes, 3a and 3b, bearing pyrazole-functionalized N-heterocyclic carbenes (NHCs) were prepared, and their structures were characterized by X-ray diffraction analysis. Given their promising anticancer potential, we evaluated the cytotoxicity of both complexes against a panel of human cancer cell lines, including breast cancer Bcap-37, colorectal cancer LoVo, gastric cancer SCG7901, and cisplatinresistant SCG7901-R cells. In vitro results showed that complex 3a inhibited cancer cell proliferation, which exhibited comparable cytotoxicity to that of clinically approved cisplatin. More impressively, complex 3a evoked significant rates of death of [a]

show abstract

Synthesis and charactrization palladium polysulfide complexes of N-heterocyclic carbenes

Cited by 6 publications

References 34 publications

Comparing the Activity of N-Heterocyclic Carbene Iron Complexes and Free Carbene Precursors in the Hydrosilylation of CO₂

Comparing the Activity of N-Heterocyclic Carbene Iron Complexes and Free Carbene Precursors in the Hydrosilylation of CO₂

Crystal structure of a dicationic Pd^II dimer containing a 2-[(diisopropylphosphanyl)methyl]quinoline-8-thiolate pincer ligand

Synthesis, Structure, Biological Evaluation, and Catalysis of Two Pyrazole‐Functionalized NHC–Ru^II Complexes

Contact Info

Product

Resources

About

Synthesis and charactrization palladium polysulfide complexes of N-heterocyclic carbenes

Cited by 6 publications

References 34 publications

Comparing the Activity of N-Heterocyclic Carbene Iron Complexes and Free Carbene Precursors in the Hydrosilylation of CO2

Comparing the Activity of N-Heterocyclic Carbene Iron Complexes and Free Carbene Precursors in the Hydrosilylation of CO2

Crystal structure of a dicationic PdII dimer containing a 2-[(diisopropylphosphanyl)methyl]quinoline-8-thiolate pincer ligand

Synthesis, Structure, Biological Evaluation, and Catalysis of Two Pyrazole‐Functionalized NHC–RuII Complexes

Contact Info

Product

Resources

About

Comparing the Activity of N-Heterocyclic Carbene Iron Complexes and Free Carbene Precursors in the Hydrosilylation of CO₂

Comparing the Activity of N-Heterocyclic Carbene Iron Complexes and Free Carbene Precursors in the Hydrosilylation of CO₂

Crystal structure of a dicationic Pd^II dimer containing a 2-[(diisopropylphosphanyl)methyl]quinoline-8-thiolate pincer ligand

Synthesis, Structure, Biological Evaluation, and Catalysis of Two Pyrazole‐Functionalized NHC–Ru^II Complexes