Publications by authors named "George Kleinhans"

The utility of carbazole in photo-, electro-, and medicinal applications has ensured its widespread use also as the backbone in tridentate pincer ligands. In this review, the aim is to identify and illustrate the key features of the -carbazolide binding to transition metal centers (with = flanking donor moieties, e.g.

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The syntheses of bis(triazolium)carbazole precursors and their corresponding coinage metal (Au, Ag) complexes are reported. For alkylated triazolium salts, di- or tetranuclear complexes with bridging ligands were isolated, while the bis(aryl) analogue afforded a bis(carbene) Au -CNC pincer complex suitable for oxidation to the redox-stable [Au (CNC)Cl] cation. Although the ligand salt and the [Au (CNC)Cl] complex were both notably cytotoxic toward the breast cancer cell line MDA-MB-231, the Au complex was somewhat more selective.

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The photophysical properties of a series of T-shaped coinage d metal complexes, supported by a bis(mesoionic carbene)carbazolide (CNC) pincer ligand, are explored. The series includes a rare new example of a tridentate T-shaped Ag complex. Post-complexation modification of the Au complex provides access to a linear cationic Au complex following ligand alkylation, or the first example of a cationic square planar Au -F complex from electrophilic attack on the metal centre.

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Article Synopsis
  • The study focuses on creating unique T-shaped Au(I) pincer complexes using a carbazole structure with mesoionic carbenes.
  • The complexes demonstrate a different reactivity than typical Au(I) complexes, showing the ability to react with electrophiles through processes like protonation and alkylation.
  • An intriguing finding is the formation of a cationic Au(III) hydride upon protonation, which is identified by a specific H NMR resonance, but it exhibits protic rather than hydridic properties.
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An air-stable rhodium(I)-oxygen adduct featuring a CNC-pincer ligand, based on 1,2,3-triazol-5-ylidenes, catalyzes the homo-dimerization and hydrothiolation of alkynes, affording the gem-enyne and α-vinyl sulfide isomers, respectively, with excellent selectivity. A one-pot stepwise strategy allows the selective catalytic preparation of non-symmetric bis-vinyl sulfides, as well as the alkyne dimerization-hydrothiolation tandem reactions.

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The synthesis and X-ray crystal structure of a potassium adduct of a monoanionic CNC-pincer ligand featuring two mesoionic carbenes is reported. Owing to the peculiar electronic and steric properties of this ligand, the first neutral stable Ni(II)-hydride, and an unusual Cu(II) complex displaying a seesaw geometry, have been isolated.

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