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

Abstract

Dinuclear silver(I) complexes with bridging Nphosphorylated 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 Nphosphorylated imidazolylidene ligands display notable catalytic efficiency in nitrene transfer reactions

Di‐ and Trinuclear Gold Complexes of Diphenylphosphinoethyl‐Functionalised Imidazolium Salts and their N‐Heterocyclic Carbenes: Synthesis and Photophysical Properties

“…A downfield resonance is seen at 172.6 ppm, which is in the typical range of gold-carbene complexes. [67] Since no signal broadening is observed in the 31 P{ 1 H} NMR spectrum or for the ethylene bridge in 1 H NMR spectrum, a mixture of products or a dimeric complex, [(L1) 2 Au 2 ]Cl 2 , similar to those described by Hofmann [44] or Kostyuk, [40] can be excluded. The EI-MS spectrum of compound 1 exhibits an ion peak for the [MÀCl] + ion including the correct isotopic pattern.…”

Copper–NHC complexes in catalysis

“…More recently, an extended scope to non-aliphatic alkenes and various functional groups was reported based on di-and tri-nuclear cationic Cu species [55]. Despite the ability to act as carbene transfer agents, the reactivity of tri-nuclear copper complexes remained inferior compared to the mono-and dinuclear analogues [56].…”

A Convenient Approach to N‐(Di‐tert‐butylphosphanyl)‐ and N‐(Di‐tert‐butylphosphoroselenoyl)formamidinium Salts: Carbene Precursors

“…The latter deprotonated salt 22 to initiate a [1,3] shift of the aminomethylene group from the selenium atom to the nitrogen atom. In contrast, the reactions of 21a and 21b (Me, iPr) led to salts 23a and 23b, but the reaction proceeded very slowly; 30 min after the reactants were mixed, the 31 P NMR spectra exhibited weak signals of the salts 23a and 23b, the starting compounds 21a and 21b, and strong signals of intermediates at δ P = 112 (22a) and 106 ppm (22b) with J P,Se 350-380 Hz, typical for P-Se single bonds.…”

“…The NHCP ligands were employed in the synthesis of transition metal complexes either from their silver complexes [3] or directly by reactions with metal salts. The NHCP ligands were employed in the synthesis of transition metal complexes either from their silver complexes [3] or directly by reactions with metal salts.…”

“…The NHCP ligands were employed in the synthesis of transition metal complexes either from their silver complexes [3] or directly by reactions with metal salts. [3] The stability of NHCP ligands A ( Figure 1) is significantly dependent on the bulkiness of the substituents at the phosphorus atom, and the di-tert-butylphosphanyl group provides the most stable ligands. [3] The stability of NHCP ligands A ( Figure 1) is significantly dependent on the bulkiness of the substituents at the phosphorus atom, and the di-tert-butylphosphanyl group provides the most stable ligands.…”