Stable N‑Phosphorylated 1,2,4-Triazol-5-ylidenes: Novel Ligands for Metal Complexes

Synthetic routes to novel N-phosphorylated 1,2,4-triazolium salts have been developed. Treatment of the specified salts with strong base produces new stable N-phosphorylated 1,2,4-triazol-5-ylidenes, which add Se in two stages (first at the carbene carbon and then at phosphorus) and rearrange to C-phosphorylated triazoles with heating. The capacity of such N-phosphorylated triazol-5-ylidenes to act as bidentate ligands toward transition-metal centers has also been demonstrated; in particular, the formation of two dinuclear silver carbene complexes is described herein. The structures of one representative carbene and of one carbene complex were determined by an X-ray study

Stable N‑Phosphorylated 1,2,4-Triazol-5-ylidenes: Novel Ligands for Metal Complexes

Synthetic routes to novel N-phosphorylated 1,2,4-triazolium salts have been developed. Treatment of the specified salts with strong base produces new stable N-phosphorylated 1,2,4-triazol-5-ylidenes, which add Se in two stages (first at the carbene carbon and then at phosphorus) and rearrange to C-phosphorylated triazoles with heating. The capacity of such N-phosphorylated triazol-5-ylidenes to act as bidentate ligands toward transition-metal centers has also been demonstrated; in particular, the formation of two dinuclear silver carbene complexes is described herein. The structures of one representative carbene and of one carbene complex were determined by an X-ray study

First Annelated Azaphosphole-Ferrocenes: Synthetic Pathways and Structures

The first annelated bis- and mono-3<i>H</i>-1,3-azaphosphole ferrocene sandwich compounds have been synthesized from aminoferrocenes, and their X-ray structures are compared to those of their selenide-protected PSe analogues, showing net discrepancies both in metallocene backbone conformation and in fused-ring planarity

First Annelated Azaphosphole-Ferrocenes: Synthetic Pathways and Structures

The first annelated bis- and mono-3<i>H</i>-1,3-azaphosphole ferrocene sandwich compounds have been synthesized from aminoferrocenes, and their X-ray structures are compared to those of their selenide-protected PSe analogues, showing net discrepancies both in metallocene backbone conformation and in fused-ring planarity

N‑Phosphorylated Azolylidenes: Novel Ligands for Dinuclear Complexes of Coinage Metals

Dinuclear silver­(I) complexes with bridging N-phosphorylated azolylidene ligands have been synthesized. Subsequent transfer of the ligands to other group 11 metal centers (Cu, Au) has been accomplished, highlighting the usefulness of the silver complexes as an easy to handle, air- and moisture-stable source of these ligands. Preliminary results indicate that dinuclear copper­(I) complexes with N-phosphorylated imidazolylidene ligands display notable catalytic efficiency in nitrene transfer reactions