Cover Feature: Isolation of Homo‐/Mixed‐Valence Ag₁₂, Ag₂₉, and Ag₈ Clusters Stabilized by Cyclic Alkyl(amino) Carbene‐Anchored Monoanionic Phosphorus Ligand (Chem. Eur. J. 64/2022)

Abstract

Cyclic alkyl(amino) carbene‐anchored monoanionic phosphorus species have been introduced as the rising ligand to stabilize three unprecedented homo (AgI)‐ and mixed (Ag0/AgI)‐valence silver nanoclusters Ag29, Ag12 and Ag8 in the solid state with defined structures. The neutral Ag29 and Ag8 clusters showed electron paramagnetic resonance at room temperature, whereas the green‐emitting tri‐cationic Ag12 cluster is diamagnetic and NMR active. More information can be found in the Research Article by S. Roy and co‐workers (DOI: 10.1002/chem.202202324).

Isolation of (Aryl)‐(Imino) Phosphide and (Aryl)‐(Phosphaalkene) Amide Complexes of Alkali Metals from Carbene‐Phosphinidenes under Reductive‐Thermal Rearrangements

“…The P atoms of the ligands are also coordinated to the Ag atom of the Ag 4 Cl 4 core, thus providing stability to the overall structure. The average P−Ag bond length is 2.436 Å, which is in well agreement with the Ag−P distances seen in our recently reported Ag clusters stabilized by cAAC‐anchored mono‐anionic phosphorous ligand [12] …”

“…The average PÀ Ag bond length is 2.436 Å, which is in well agreement with the AgÀ P distances seen in our recently reported Ag clusters stabilized by cAAC-anchored mono-anionic phosphorous ligand. [12] The AgÀ Cl bond length of the Ag 4 Cl 4 core is in the range of 2.55-2.83 Å. This complex features the shortest C46À N3 bond distance of 1.251 (12) Å among all the complexes discussed here.…”

“…[12] The AgÀ Cl bond length of the Ag 4 Cl 4 core is in the range of 2.55-2.83 Å. This complex features the shortest C46À N3 bond distance of 1.251 (12) Å among all the complexes discussed here.…”

“…[11] Recently, it has been shown that the alkali metal phosphinidenides (E-G) can be utilized as the source of carbene-supported mono-anionic phosphorus; an excellent ligand with three available lone pairs of electrons on the P atom, and thereby capable of μ 3 -P type coordination to the metal centres (Scheme 1). [12] Herein, we report on the alkali metal mediated reductive dehalogenation of carbene-chloro-phosphinidenes (1), followed by unprecedented thermal rearrangements [13] leading to either thermodynamically favored migration of the dipp group (dipp = 2,6-diisopropylphenyl) [14] from the N to the P centre of 1 (I) or the cleavage of the CMe 2 À N bond of the five-membered ring of cAAC ligand in 1, and the subsequent ring-closure in presence of the P À generated in situ to form a new five-membered ring containing the divalent phosphorus as the heteroatom (J), generating the alkali metal complexes of (aryl)-(cyclic alkyl(imino)) phosphides (3 a-3 c, 4 a-4 b), and (aryl)-(cyclic alkyl(phosphaalkene)) amide (5; Scheme 1, aryl = dipp group).…”

“…Recently, it has been shown that the alkali metal phosphinidenides ( E – G ) can be utilized as the source of carbene‐supported mono‐anionic phosphorus; an excellent ligand with three available lone pairs of electrons on the P atom, and thereby capable of μ 3 ‐P type coordination to the metal centres (Scheme 1). [12] …”